WO2016147318A1 - 粘着性組成物、粘着剤および粘着シート - Google Patents
粘着性組成物、粘着剤および粘着シート Download PDFInfo
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- WO2016147318A1 WO2016147318A1 PCT/JP2015/057920 JP2015057920W WO2016147318A1 WO 2016147318 A1 WO2016147318 A1 WO 2016147318A1 JP 2015057920 W JP2015057920 W JP 2015057920W WO 2016147318 A1 WO2016147318 A1 WO 2016147318A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, a method for producing a pressure-sensitive adhesive composition, a pressure-sensitive adhesive (a material obtained by crosslinking the pressure-sensitive adhesive composition), and a pressure-sensitive adhesive sheet, and in particular, for a protective sheet for optical members such as polarizing plates.
- a pressure-sensitive adhesive composition a method for producing a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet.
- high-speed adhesive force When the adhesive sheet is used for the purpose of quickly peeling from the adherend, it is suitable that the adhesive force in high-speed peeling (hereinafter sometimes referred to as “high-speed adhesive force”) is relatively small.
- a protective sheet for protecting the surface may be attached to at least one surface of the polarizing plate.
- the protective sheet is peeled from the polarizing plate, it is advantageous from the viewpoint of workability that the protective sheet can be peeled quickly without requiring a large force.
- the size of the polarizing plate is increased, the area to be peeled is widened, and the demand for a pressure-sensitive adhesive sheet having a small high-speed adhesive force is increasing.
- the pressure-sensitive adhesive force in the low-speed peeling (hereinafter referred to as “the pressure-sensitive adhesive sheet” will not be unintentionally peeled off from the adherend) It may be necessary to have sufficient (sometimes referred to as “slow adhesion”). Therefore, there is a demand for an adhesive sheet that has both a relatively small high-speed adhesive force and a sufficient low-speed adhesive force.
- the pressure-sensitive adhesive sheet having such properties can be obtained by using a pressure-sensitive adhesive obtained by crosslinking a pressure-sensitive adhesive composition containing an acrylic polymer, a crosslinking agent and a tin catalyst.
- a tin catalyst by using a tin catalyst, the high-speed adhesive force can be reduced and the low-speed adhesive force can be maintained to a certain level.
- the pressure-sensitive adhesive sheet thus obtained contains a tin compound and has a problem of environmental burden.
- Citations 1 and 2 disclose an adhesive sheet manufactured without using a tin compound.
- a zirconium compound is used instead of the tin compound (claim 1 of the cited document 1).
- a metal organic compound containing bismuth or the like is used as a crosslinking accelerator (Claims 1 and 2 of Cited Document 2).
- Cited Document 1 when a zirconium compound is used as in Cited Document 1, the pressure-sensitive adhesive force cannot be sufficiently reduced, and a pressure-sensitive adhesive sheet having a relatively small high-speed pressure-sensitive adhesive force cannot be obtained. Moreover, when a bismuth compound is used like the cited reference 2, while low speed adhesive force falls, high speed adhesive force does not fully fall. Therefore, it has been difficult to produce a pressure-sensitive adhesive sheet that has both a relatively small high-speed adhesive force and a sufficient low-speed adhesive force without using a tin compound.
- the present invention has been made in view of such a situation, and a pressure-sensitive adhesive composition capable of obtaining a pressure-sensitive adhesive sheet having a relatively small high-speed pressure-sensitive adhesive force and sufficient low-speed pressure-sensitive adhesive force, and production of the pressure-sensitive adhesive composition It aims at providing a method, an adhesive, and the said adhesive sheet.
- the present invention provides a first (meth) acrylic acid ester copolymer containing a monomer having a hydroxyl group and a monomer having a carboxyl group as a monomer unit constituting the copolymer.
- A a monomer having a weight average molecular weight smaller than the weight average molecular weight of the first (meth) acrylic acid ester copolymer (A), and having a hydroxyl group as a monomer unit constituting the copolymer
- a pressure-sensitive adhesive composition containing a second (meth) acrylic acid ester copolymer (B) containing a monomer having a carboxyl group and an isocyanate crosslinking agent (C), wherein the second (meth) )
- the proportion of the monomer having the hydroxyl group in the monomer constituting the acrylic ester copolymer (B) is the first (meth) acrylic ester.
- the pressure-sensitive adhesive composition is characterized in that the blending ratio based on the mass of the (meth) acrylic acid ester copolymer (B) is 90:10 to 10:90 (Invention 1).
- the low molecular weight copolymer (B) has more hydroxyl groups as crosslinking points than the high molecular weight copolymer (A).
- a pressure-sensitive adhesive sheet having a relatively small high-speed adhesive force and sufficient low-speed adhesive force can be obtained.
- the first (meth) acrylic acid ester copolymer (A) has a weight average molecular weight of 50,000 to 500,000, and the second (meth) acrylic acid ester copolymer
- the weight average molecular weight of the combined body (B) is preferably 20,000 to 100,000 (Invention 2).
- the first (meth) acrylic acid ester copolymer (A) contains 0.01 to 5 mass of a monomer having a hydroxyl group as a monomer unit constituting the copolymer. % (Invention 3).
- the second (meth) acrylic acid ester copolymer (B) contains 0.1 to 10 mass of a monomer having a hydroxyl group as a monomer unit constituting the copolymer. % (Invention 4).
- the second (meth) acrylic acid ester copolymer (B) preferably contains ethylene oxide as a monomer unit constituting the copolymer (Invention 5).
- the adhesive composition does not contain a tin compound (Invention 6).
- the present invention is a method for producing the above-mentioned pressure-sensitive adhesive composition (Invention 1 to 6), wherein the monomer constituting the first (meth) acrylic acid ester copolymer (A) is converted into a conversion rate.
- the step (2) for producing the second (meth) acrylic acid ester copolymer (B) by radical copolymerization under the above, and the step (3) for adding the isocyanate-based crosslinking agent (C) A method for producing a pressure-sensitive adhesive composition, comprising: Subjected to (invention 7).
- invention 7 in the process (2) which manufactures said 2nd (meth) acrylic acid ester copolymer (B), said 1st (meth) acrylic acid ester copolymer (A) It is preferable to radically polymerize the monomer remaining during the polymerization of the monomer and the monomer constituting the second (meth) acrylic acid ester copolymer (B) at a conversion rate of 70 to 100% (Invention 8).
- the present invention provides a pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition (Invention 1 to 6) (Invention 9).
- this invention is an adhesive sheet provided with the base material and the adhesive layer, Comprising:
- the said adhesive layer consists of the said adhesive (invention 9),
- the adhesive sheet characterized by the above-mentioned is provided.
- Invention 10 The adhesive sheet characterized by the above-mentioned.
- the pressure-sensitive adhesive sheet is preferably a protective sheet for protecting the adherend (Invention 11).
- the adherend is preferably an optical member (Invention 12).
- a pressure-sensitive adhesive composition that does not contain a tin compound and can obtain a pressure-sensitive adhesive sheet having a relatively small high-speed pressure-sensitive adhesive strength and sufficient low-speed pressure-sensitive adhesive strength, a method for producing the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive, In addition, the pressure-sensitive adhesive sheet can be obtained.
- the pressure-sensitive adhesive composition comprises a first (meth) acrylic acid ester copolymer (A), a second (meth) acrylic acid ester copolymer (B), and an isocyanate crosslinking agent ( C).
- (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms.
- the first (meth) acrylic acid ester copolymer (A) is a monomer having a hydroxyl group and a monomer having a carboxyl group as monomer units constituting the copolymer. Containing.
- the second (meth) acrylic acid ester copolymer (B) has a weight average molecular weight smaller than the weight average molecular weight of the first (meth) acrylic acid ester copolymer (A).
- a monomer unit to be constituted a monomer having a hydroxyl group and a monomer having a carboxyl group are contained.
- the proportion of the monomer having a hydroxyl group in the monomer constituting the second (meth) acrylic acid ester copolymer (B) is the first (meth) acrylic acid ester. It is larger than the ratio of the monomer having a hydroxyl group in the monomer constituting the copolymer (A).
- the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B) are composed of 100 parts by mass of the total number of parts by mass of the first (meth) acrylic acid ester copolymer (B).
- the total number of parts by weight of the monomer having a carboxyl group constituting the (meth) acrylate copolymer (A) and the second (meth) acrylate copolymer (B) is 0.1 to 1.0 mass. Part.
- the blending ratio based on the mass of the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B) is 90:10 to 10:90. is there.
- the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B) are each a copolymer.
- a monomer having a carboxyl group is contained as a constituent monomer unit.
- the monomer having a carboxyl group acts as a crosslinking accelerator. Therefore, in the pressure-sensitive adhesive composition according to this embodiment, the monomer having a carboxyl group is contained in the copolymer (A) and the copolymer (B) as a monomer constituent unit, thereby promoting other crosslinking such as a tin catalyst.
- the use of the agent can be omitted.
- the total number of parts by weight of the monomer having a carboxyl group constituting the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B) is 100 parts by mass.
- the total is 0.1 to 1.0 part by mass, preferably 0.15 to 0.8 part by mass, and particularly preferably 0.30 to 0.6 part by mass.
- the crosslinking reaction is excessively promoted, and the adhesive composition is prevented from gelling before the formation of the adhesive, Sufficient pot life can be secured.
- the total number of parts by mass of the monomers having a carboxyl group is 0.1 parts by mass or more, the effect of promoting crosslinking can be obtained.
- the first (meth) acrylic acid ester copolymer (A) preferably contains 0.01 to 2.00% by mass of a monomer having a carboxyl group as a monomer unit constituting the copolymer.
- the content is preferably 0.05 to 1.50% by mass, and more preferably 0.30 to 1.00% by mass.
- the pot life of the adhesive composition becomes more excellent.
- the content of the monomer is 0.01% by mass or more, the effect of promoting crosslinking by a carboxyl group can be sufficiently obtained, and thereby, the crosslinked structure formed mainly of the copolymer (B). In part, the structure in which the copolymer (A) is bonded via a hydroxyl group is well formed, and the high-speed adhesive force of the resulting adhesive sheet can be kept low.
- the second (meth) acrylic acid ester copolymer (B) preferably contains 0.01 to 0.99% by mass of a monomer having a carboxyl group as a monomer unit constituting the copolymer.
- the content is preferably 0.05 to 0.80% by mass, and more preferably 0.20 to 0.60% by mass.
- the pot life of an adhesive composition becomes more excellent because content of the said monomer is 0.99 mass% or less.
- the content of the monomer is 0.01% by mass or more, an effect of promoting crosslinking by a carboxyl group is obtained, whereby a good crosslinked structure is formed, and the resulting adhesive sheet has a high-speed adhesive force. It can be kept low.
- Examples of the monomer having a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, and vinyl acetate. These may be used alone or in combination of two or more. From the viewpoint of promoting crosslinking, it is particularly preferable to use acrylic acid as a monomer having a carboxyl group.
- the first (meth) acrylate copolymer (A) and the second (meth) acrylate copolymer (B) are each a copolymer.
- a monomer having a hydroxyl group is contained as a constituent monomer unit. Since the pressure-sensitive adhesive composition according to this embodiment contains an isocyanate-based crosslinking agent (C) as a crosslinking agent, a hydroxyl group having excellent reactivity with an isocyanate group is used as a crosslinking point in the copolymers (A) and (B). Works.
- the proportion of the monomer having a hydroxyl group in the monomer constituting the second (meth) acrylic acid ester copolymer (B) is the first (meth) acrylic acid ester copolymer weight. It is larger than the ratio of the monomer having a hydroxyl group in the monomer constituting the combined body (A).
- the copolymer (B) tends to restrain the copolymer (A) at the time of high-speed peeling. Power is sufficiently reduced.
- the first (meth) acrylic acid ester copolymer (A) preferably contains 0.01 to 5% by mass of a hydroxyl group-containing monomer as a monomer unit constituting the copolymer, particularly 0.05.
- the content is preferably 1 to 1% by mass, and more preferably 0.1 to 0.5% by mass.
- the second (meth) acrylic acid ester copolymer (B) preferably contains 0.1 to 10% by mass of a hydroxyl group-containing monomer as a monomer unit constituting the copolymer, particularly 0.6. It is preferably contained in an amount of ⁇ 8% by mass, more preferably 1.1 ⁇ 5% by mass.
- Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( And (meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. These may be used alone or in combination of two or more.
- 4-hydroxybutyl acrylate exhibits high reactivity in the cross-linking reaction, and therefore 4-hydroxybutyl acrylate is preferably used as a monomer having a hydroxyl group from the viewpoint of easily reducing high-speed adhesive strength. .
- the second (meth) acrylic acid ester copolymer (B) has a (meth) acrylic acid ester having an alkylene oxide chain as a monomer unit constituting the copolymer ( Hereinafter, it may also be referred to as an alkylene oxide chain-containing acrylic acid ester).
- the alkylene of the alkylene oxide chain is preferably alkylene having 2 to 4 carbon atoms, and particularly preferably ethylene oxide having 2 carbon atoms.
- the average number of added moles of the alkylene oxide chain in one molecule of the alkylene oxide chain-containing acrylate ester is preferably 1 to 20 moles, particularly preferably 3 to 15 moles, and more preferably 6 to 10 moles. Mole is preferred.
- the second (meth) acrylic acid ester copolymer (B) contains an alkylene oxide chain-containing (meth) acrylic acid ester as a monomer unit
- an ion conductive antistatic agent is added to this adhesive.
- the mobility of the antistatic agent in the pressure-sensitive adhesive is increased, so that the effect of the antistatic agent can be further obtained.
- the first (meth) acrylic acid ester copolymer (A) may contain an alkylene oxide chain-containing (meth) acrylic acid ester as a monomer unit constituting the copolymer. Due to the high molecular weight of (A), the viscosity of the pressure-sensitive adhesive composition may increase too much, and the processability may deteriorate.
- the alkylene oxide chain-containing (meth) acrylic acid ester is contained only in the second (meth) acrylic acid ester copolymer (B).
- the end of the alkylene oxide chain is preferably protected with an alkyl group having 1 to 4 carbon atoms so as not to react with the crosslinking agent.
- the copolymer (B) contains an alkylene oxide chain (meta) as a monomer unit.
- Acrylic acid ester is preferably contained in an amount of 1 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 10 to 17% by mass.
- the first (meth) acrylate copolymer (A) and the second (meth) acrylate copolymer (B) are each a copolymer.
- the monomer unit constituting it is preferable to contain a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms.
- (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group examples include, for example, methyl acrylate and ethyl (meth) acrylate.
- (meth) acrylic acid alkyl ester having 4 to 8 carbon atoms in the alkyl group examples include butyl acrylate and acrylic acid 2-acrylate. Ethyl hexyl is mentioned. In particular, it is preferred to use both butyl acrylate and 2-ethylhexyl acrylate.
- the first (meth) acrylic acid ester copolymer (A) and the first 2 (meth) acrylic acid ester copolymer (B) preferably contains 60 to 99.8% by mass of (meth) acrylic acid alkyl ester as a monomer constituent unit. Further, the copolymer (A) more preferably contains 85 to 99.6% by mass of (meth) acrylic acid alkyl ester as a monomer constituent unit. The copolymer (B) more preferably contains 65 to 85% by mass of a (meth) acrylic acid alkyl ester as a monomer constituent unit.
- the first (meth) acrylic acid is used from the viewpoint of achieving both low-speed adhesive strength and high-speed adhesive strength.
- the ratio of 2-ethylhexyl acrylate to butyl acrylate in each of the ester copolymer (A) and the second (meth) acrylic ester copolymer (B) is 95: 5 to 50:50 in terms of mass. In particular, 90:10 to 60:40 is preferable. In the copolymer (A), the ratio is more preferably 74:26 to 65:35 in terms of mass. In the copolymer (B), the ratio is more preferably 85:15 to 76:24 in terms of mass.
- the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B) are, if desired, the polymer.
- Other monomer may be contained as a monomer unit that constitutes.
- the other monomer is preferably a monomer that does not contain a reactive functional group in order not to interfere with the action of the monomer having a carboxyl group and the monomer having a hydroxyl group.
- alkoxyalkyl group-containing (meth) acrylic such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
- Acid ester (meth) acrylic acid phenyl, (meth) acrylic acid ester having an aromatic ring such as benzyl (meth) acrylate, silicone (meth) acrylate, acrylic acid ester such as fluorine (meth) acrylate, acrylamide, methacryl Non-crosslinkable acrylamide such as amide and acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc.
- (Meth) acrylic acid ester, vinyl acetate N- vinylpyrrolidone and vinyl monomers such as styrene and the like. These may be used alone or in combination of two or more.
- the first (meth) acrylic acid ester copolymer (A) may be used singly or in combination of two or more.
- said 2nd (meth) acrylic acid ester type copolymer (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the second (meth) acrylic acid ester copolymer (B) has a crosslinking point more than the first (meth) acrylic acid ester copolymer (A).
- the weight average molecular weight of the 2nd (meth) acrylic acid ester copolymer (B) is smaller than the weight average molecular weight of the 1st (meth) acrylic acid ester copolymer (A).
- the weight average molecular weight of the first (meth) acrylic acid ester copolymer (A) is preferably 50,000 to 500,000, particularly preferably 100,000 to 400,000, and more preferably 150,000 to 30 It is preferable to be 10,000.
- the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the weight average molecular weight of the second (meth) acrylic acid ester copolymer (B) is preferably 20,000 to 100,000, particularly preferably 50,000 to 50,000, It is preferably 10,000 to 20,000.
- the pressure-sensitive adhesive composition blending based on the mass of the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B).
- the ratio is 90:10 to 10:90.
- the amount of the second (meth) acrylic acid ester copolymer (B) is preferably larger than the amount of the first (meth) acrylic acid ester copolymer (A).
- the blending ratio is preferably 45:55 to 10:90, particularly preferably 42:58 to 20:80, and more preferably 40:60 to 30:70.
- the isocyanate-based crosslinking agent (C) contains at least a polyisocyanate compound.
- the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate.
- biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like.
- low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like.
- an isocyanurate type trimer of 1,6-hexamethylene diisocyanate may be used individually by 1 type and may be used in combination of 2 or more type.
- the content of the isocyanate-based crosslinking agent (C) is 100 parts by mass in total of the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B).
- the amount is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 8 parts by weight, and more preferably 2 to 6 parts by weight.
- the pressure-sensitive adhesive composition according to this embodiment may contain a plasticizer. By containing a plasticizer, the adhesive force of the obtained adhesive can be easily controlled.
- plasticizer examples include tributyl acetyl citrate and tetraethylene glycol dimethyl ether.
- the content of the plasticizer is 1 to 20 with respect to 100 parts by mass in total of the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B).
- the amount is preferably 3 parts by mass, particularly preferably 3 to 15 parts by mass, and more preferably 6 to 12 parts by mass.
- various additives usually used for acrylic adhesives for example, tackifiers, antioxidants, ultraviolet absorbers, light stabilizers, softeners, fillers, antistatic agents, are optionally used.
- An agent, a refractive index adjusting agent, etc. can be added.
- the adhesive composition according to this embodiment preferably does not contain a tin compound.
- the pressure-sensitive adhesive composition according to this embodiment preferably does not contain an organotin compound.
- a tin compound such as a tin catalyst as a crosslinking accelerator.
- the adhesive composition does not contain a tin compound, it is possible to obtain an adhesive having a reduced load on the environment.
- the adhesive composition according to this embodiment can be produced, for example, as follows.
- the (meth) acrylic acid ester copolymers (A) and (B) are prepared separately by a normal radical polymerization method, preferably in a polymerization solvent described later.
- the obtained solutions of both copolymers are mixed, and a diluting solvent is added so that the solid concentration is 10 to 40% by mass.
- an isocyanate-based crosslinking agent (C) is added and mixed thoroughly to obtain a pressure-sensitive adhesive composition diluted with a solvent.
- the above-mentioned adhesive composition is preferably produced by the following series of polymerizations.
- the monomer constituting the first (meth) acrylic acid ester copolymer (A) contained in the mixed liquid (a) is as described above. Further, the content of the monomer having a carboxyl group, the monomer having a hydroxyl group, and the (meth) acrylic acid alkyl ester in the mixed liquid (a) is the same as that of the first (meth) acrylic acid ester copolymer (A). It can be made the same as content mentioned above as a monomer unit to comprise.
- the monomers constituting the second (meth) acrylic acid ester copolymer (B) contained in the mixed liquid (b) are as described above.
- the content of the carboxyl group-containing monomer, the hydroxyl group-containing monomer, the alkylene oxide chain-containing (meth) acrylic acid ester and the (meth) acrylic acid alkyl ester in the mixed liquid (b) is respectively ) It may be the same as the content described above as the monomer unit constituting the acrylate copolymer (B).
- the mixing ratio of the mixed liquid (a) and the mixed liquid (b) is preferably 90:10 to 10:90 in terms of mass.
- the blending amount of the mixed solution (b) is preferably larger than the blending amount of the mixed solution (a).
- the blending ratio is preferably 45:55 to 10:90, particularly It is preferably 42:58 to 20:80, more preferably 40:60 to 30:70.
- the isocyanate-based crosslinking agent (C) and the plasticizer are as described above.
- the compounding quantity of an isocyanate type crosslinking agent (C) and a plasticizer may respectively be the same as the quantity mentioned above as content in an adhesive composition.
- the above-mentioned amount of the isocyanate-based crosslinking agent (C) or the plasticizer can be used.
- the above-described series polymerization can be performed by a solution polymerization method using a polymerization initiator as desired.
- the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like, and two or more kinds may be used in combination.
- Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more kinds may be used in combination.
- Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
- organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
- organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxy.
- examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
- the pressure-sensitive adhesive according to this embodiment is obtained by crosslinking the pressure-sensitive adhesive composition.
- Crosslinking of the pressure-sensitive adhesive composition can be performed by heat treatment.
- this heat processing can also serve as the drying process at the time of volatilizing the dilution solvent etc. of an adhesive composition.
- the heating temperature is preferably 50 to 150 ° C., particularly preferably 70 to 120 ° C.
- the heating time is preferably 30 seconds to 3 minutes, particularly preferably 50 seconds to 2 minutes. Further, it is particularly preferable to provide a curing period of about 1 to 2 weeks at room temperature (for example, 23 ° C., 50% RH) after the heat treatment.
- the first (meth) acrylic acid ester copolymer (A) and the second (meth) acrylic acid ester copolymer (B) by the isocyanate-based crosslinking agent (C). are crosslinked to form a three-dimensional network structure.
- the second (meth) acrylic acid ester copolymer (B) since the second (meth) acrylic acid ester copolymer (B) has more crosslinking points, the second (meth) acrylic acid ester copolymer (B) is preferentially crosslinked.
- the adhesive described above can be preferably used for optical members.
- it can be preferably used as an adhesive layer of a protective sheet for protecting an optical member.
- a polarizing plate is mentioned as an example of an optical member.
- the pressure-sensitive adhesive sheet 1 As shown in FIG. 1, the pressure-sensitive adhesive sheet 1 according to the present embodiment is laminated on the pressure-sensitive adhesive layer 11, the release sheet 12, the pressure-sensitive adhesive layer 11 stacked on the release surface of the release sheet 12, from the bottom. And a base material 13.
- the release surface of the release sheet in this specification refers to a surface having peelability in the release sheet, and includes both a surface that has been subjected to a release treatment and a surface that exhibits peelability without being subjected to a release treatment. .
- the pressure-sensitive adhesive layer 11 is made of a pressure-sensitive adhesive obtained by crosslinking the above-described pressure-sensitive adhesive composition. For this reason, the pressure-sensitive adhesive sheet 1 according to the present embodiment has a relatively low high-speed adhesive force and sufficiently has a low-speed adhesive force.
- the pressure-sensitive adhesive sheet 1 according to this embodiment is preferably for protecting the adherend. That is, the pressure-sensitive adhesive sheet 1 is preferably a protective sheet.
- the adherend include an optical member.
- the optical member include a polarizing plate (polarizing film), a polarizer, a retardation plate (retarding film), a viewing angle compensation film, a brightness enhancement film, and a contrast enhancement film.
- the pressure-sensitive adhesive sheet 1 according to this embodiment has a relatively low high-speed pressure-sensitive adhesive force and sufficiently has a low-speed pressure-sensitive adhesive force, and thus is particularly suitable for an application that quickly peels off an adherend like a protective sheet.
- the thickness of the pressure-sensitive adhesive layer 11 is appropriately determined according to the purpose of use of the pressure-sensitive adhesive sheet 1 and is usually in the range of 2 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
- the pressure-sensitive adhesive sheet is an optical member, particularly a polarizing plate.
- the thickness is preferably 5 to 30 ⁇ m, particularly 10 to 25 ⁇ m.
- a plastic film made of a resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polycarbonate, polymethylpentene, polyphenylene sulfide, liquid crystal polymer, and the like is preferable.
- a film may be sufficient and the film which laminated
- a polyethylene terephthalate film is particularly preferable.
- the said plastic film may contain additives, such as a heat resistance improver and a ultraviolet absorber other than a filler.
- a surface treatment by an oxidation method or a concavo-convex method or a primer treatment can be applied as desired.
- the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like.
- Examples include a thermal spraying method.
- the base material 13 is preferably transparent or translucent. Since the base material 13 is transparent or translucent, when the pressure-sensitive adhesive sheet 1 is used as a protective sheet, it is possible to confirm the application surface on the adherend while the protective sheet is attached to the adherend. Become.
- the thickness of the base material 13 can be set according to the application of the pressure-sensitive adhesive sheet, but is preferably 5 to 300 ⁇ m, and particularly preferably 10 to 200 ⁇ m. In particular, when the pressure-sensitive adhesive sheet is a protective sheet, the thickness is preferably 15 to 150 ⁇ m, and particularly preferably 20 to 80 ⁇ m.
- Examples of the release sheet 12 include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, and polybutylene terephthalate film.
- a liquid crystal polymer film or the like is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.
- the release surface of the release sheet (particularly the surface in contact with the pressure-sensitive adhesive layer 11) is preferably subjected to a release treatment.
- the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
- the thickness of the release sheet 12 is not particularly limited, but is usually about 20 to 150 ⁇ m.
- the pressure-sensitive adhesive sheet 1 according to this embodiment has a relatively small pressure-sensitive adhesive force when peeled at a high speed.
- the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer when peeling at a speed of 30 m / min is preferably 300 to 2000 mN / 25 mm, and particularly preferably 400 to 1500 mN / 25 mm. More preferably, it is 500 to 1000 mN / 25 mm.
- the pressure-sensitive adhesive sheet 1 according to this embodiment has a sufficiently large pressure-sensitive adhesive force when peeled at a low speed.
- the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer when peeling at a speed of 0.3 m / min is preferably 20 to 200 mN / 25 mm, particularly 40 to 150 mN / 25 mm. More preferably, it is preferably 50 to 120 mN / 25 mm.
- a solution containing the pressure-sensitive adhesive composition is applied to the release surface of the release sheet 12, and heat treatment is performed to form the pressure-sensitive adhesive layer 11.
- the base material 13 is laminated. The conditions for the heat treatment are as described above.
- Examples of the diluent solvent for diluting the adhesive composition to form a coating solution include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, methylene chloride, and ethylene chloride.
- Halogenated hydrocarbons alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, esters such as ethyl acetate and butyl acetate, ethyl cellosolve Cellosolve solvents such as are used.
- the concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, it is diluted so that the concentration of the adhesive composition is 10 to 40% by mass.
- addition of a dilution solvent etc. is not a necessary condition, and if a viscosity etc. which can be coated with an adhesive composition, it is not necessary to add a dilution solvent. In this case, the adhesive composition becomes the coating solution as it is.
- a bar coating method for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
- the above pressure-sensitive adhesive sheet 1 has a relatively low high-speed adhesive force and sufficient low-speed adhesive force, and therefore has excellent workability when the pressure-sensitive adhesive sheet 1 is quickly peeled off from the adherend.
- the base material 13 of the adhesive sheet 1 may be omitted.
- the release sheet 12 of the pressure-sensitive adhesive sheet 1 may be omitted.
- Example 1 Process (1) 100 parts by mass of a mixed solution (a) of 68.04 parts by mass of 2-ethylhexyl acrylate, 30.46 parts by mass of butyl acrylate, 0.23 parts by mass of 4-hydroxybutyl acrylate and 1.27 parts by mass of acrylic acid And 40 mass parts was fractionated and copolymerized by the solution polymerization method, and the 1st (meth) acrylic acid ester copolymer (A) was prepared. When the molecular weight of this polymer (A) was measured using the gel permeation chromatography (GPC) mentioned later, it was weight average molecular weight (Mw) 180,000. Further, the conversion rate at this time (a value obtained by dividing the mass of the copolymer obtained by polymerizing the monomer by the total mass of the monomer used as a raw material) was 80%.
- GPC gel permeation chromatography
- Process (3) 100 parts by mass in terms of solid content of the acrylic polymer solution obtained in the above step (2) was collected and diluted with methyl ethyl ketone so that the solid content concentration was 20% by mass. Then, 3.5 parts by mass of an isocyanurate-type trimer of 1,6-hexamethylene diisocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate HX”) was added as the isocyanate-based crosslinking agent (C). By stirring, a diluted solution of the adhesive composition was obtained.
- the diluted solution of the obtained adhesive composition was coated with a knife coater on the release treated surface of a release sheet (SP-PET3811, thickness: 38 ⁇ m, manufactured by Lintec Co., Ltd.) obtained by releasing one side of a polyethylene terephthalate film with a silicone release agent. After the application, heat treatment was performed at 90 ° C. for 1 minute to form an adhesive layer having a thickness of 25 ⁇ m.
- a release sheet SP-PET3811, thickness: 38 ⁇ m, manufactured by Lintec Co., Ltd.
- a 38 ⁇ m-thick polyethylene terephthalate film as a base material was bonded to the surface of the pressure-sensitive adhesive layer opposite to the release sheet, and cured at 23 ° C. and 50% RH for 7 days to obtain a pressure-sensitive adhesive sheet. .
- Examples 2 to 4 Comparative Examples 1 to 10
- the composition of the mixed liquids (a) and (b) was changed as shown in Table 1, and the isocyanate-based crosslinking agent (C), reaction inhibitor, crosslinking accelerator and plasticizer were changed as shown in Table 2.
- a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that it was added.
- the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene measured (GPC measurement) using gel permeation chromatography (GPC) under the following conditions.
- GPC measurement device manufactured by Tosoh Corporation, HLC-8020 GPC column (passed in the following order): TSK guard column HXL-H manufactured by Tosoh Corporation TSK gel GMHXL ( ⁇ 2) TSK gel G2000HXL ⁇ Measurement solvent: Tetrahydrofuran ⁇ Measurement temperature: 40 ° C.
- Table 1 shows the composition of the mixed solution (a) prepared in the step (1) and the mixed solution (b) prepared in the step (2) and the blending ratio of the mixed solution (a) and the mixed solution (b).
- Table 2 shows the compositions of the copolymers (A) and (B) derived from the composition of the mixed solution in Table 1 and the blending amounts of other components. The details of the abbreviations described in Tables 1 and 2 are as follows.
- Test Example 1 (Measurement of low-speed adhesive strength and high-speed adhesive strength) The release sheet was peeled off from the pressure-sensitive adhesive sheet obtained in Example or Comparative Example, and the exposed pressure-sensitive adhesive layer was bonded to the saponification-treated surface of a triacetyl cellulose film having a thickness of 80 ⁇ m on which one surface was saponified. Then, it was pressurized at 0.5 MPa and 50 ° C. for 20 minutes in an autoclave manufactured by Kurihara Seisakusho. Thereafter, a sample having a width of 50 mm and a length of 120 mm was cut out from the laminate.
- the sample was allowed to stand for 24 hours under conditions of normal pressure, 23 ° C., and 50% RH, and then peeled using a tensile tester (Orientec, Tensilon) in accordance with JIS Z 0237: 2009.
- the adhesive strength (N / 25 mm) was measured under the conditions of 300 mm / min and peeling angle of 180 degrees. The measurement results are shown in Table 3 as low speed adhesive strength.
- the sample is allowed to stand for 24 hours under conditions of normal pressure, 23 ° C., and 50% RH, and then, using a tensile tester (Orientec, Tensilon), in accordance with JIS Z 0237: 2009,
- the adhesive strength (N / 25 mm) was measured under the conditions of a peeling speed of 30 m / min and a peeling angle of 180 degrees.
- the measurement results are shown in Table 3 as high-speed adhesive strength.
- the pressure-sensitive adhesive sheet according to the example showed a low high-speed pressure-sensitive adhesive force as compared with the pressure-sensitive adhesive sheet according to the comparative example.
- the pressure-sensitive adhesive sheets according to the examples showed sufficient low-speed pressure-sensitive adhesive strength although they tend to be lower than the pressure-sensitive adhesive sheets according to the comparative examples.
- the adhesive composition which concerns on an Example showed the acceptable pot life, and especially the adhesive composition which concerns on Examples 2-4 showed the outstanding pot life.
- Comparative Examples 1 to 5 and 7 showed very high high-speed adhesive strength.
- Comparative Examples 6 and 8 to 10 the pot life of the pressure-sensitive adhesive composition was very short and gelled before forming the pressure-sensitive adhesive layer, making it impossible to produce a pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive composition and pressure-sensitive adhesive of the present invention are suitable for bonding a protective sheet to an optical member such as a polarizing plate, and the pressure-sensitive adhesive sheet of the present invention is suitable as a protective sheet for an optical member such as a polarizing plate. is there.
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Abstract
Description
本実施形態に係る粘着性組成物は、第1の(メタ)アクリル酸エステル共重合体(A)と、第2の(メタ)アクリル酸エステル共重合体(B)と、イソシアネート系架橋剤(C)とを含有する。なお、本明細書において、(メタ)アクリル酸エステルとは、アクリル酸エステル及びメタクリル酸エステルの両方を意味する。他の類似用語も同様である。
本実施形態に係る粘着性組成物は、例えば、以下のようにして製造することができる。
(1)第1の(メタ)アクリル酸エステル共重合体(A)を構成するモノマーを含有する混合液(a)において、転化率50~90%でラジカル重合して、第1の(メタ)アクリル酸エステル共重合体(A)を製造した後、
(2)第2の(メタ)アクリル酸エステル共重合体(B)を構成するモノマーを含有する混合液(b)を添加し、当該モノマーと第1の(メタ)アクリル酸エステル共重合体(A)の重合時に残留するモノマーとを、上記第1の(メタ)アクリル酸エステル共重合体(A)の存在下で、好ましくは転化率70~100%でラジカル共重合して、第2の(メタ)アクリル酸エステル共重合体(B)を製造し、次いで、
(3)イソシアネート系架橋剤(C)、ならびに所望により可塑剤および各種添加剤を添加する。
本実施形態に係る粘着剤は、上記粘着性組成物を架橋してなるものである。上記粘着性組成物の架橋は、加熱処理により行うことができる。なお、この加熱処理は、粘着性組成物の希釈溶媒等を揮発させる際の乾燥処理で兼ねることもできる。
図1に示すように、本実施形態に係る粘着シート1は、下から順に、剥離シート12と、剥離シート12の剥離面に積層された粘着剤層11と、粘着剤層11に積層された基材13とから構成される。なお、本明細書における剥離シートの剥離面とは、剥離シートにおいて剥離性を有する面をいい、剥離処理を施した面および剥離処理を施さなくても剥離性を示す面のいずれをも含むものである。
1.工程(1)
アクリル酸2-エチルヘキシル68.04質量部、アクリル酸ブチル30.46質量部、アクリル酸4-ヒドロキシブチル0.23質量部およびアクリル酸1.27質量部の混合液(a)100質量部を調製し、その40質量部を分取し溶液重合法により共重合させて、第1の(メタ)アクリル酸エステル共重合体(A)を調製した。この重合体(A)の分子量を後述するゲルパーミエーションクロマトグラフィー(GPC)を用いて測定したところ、重量平均分子量(Mw)18万であった。また、このときの転化率(モノマーを重合して得られる共重合体の質量を、原料として用いたモノマーの総質量で除した値)は、80%であった。
アクリル酸2-エチルヘキシル65.25質量部、アクリル酸ブチル12.99質量部、メトキシ末端を有するエチレンオキシド鎖(平均付加モル数=9モル)含有アクリル酸エステル16.23質量部、アクリル酸4-ヒドロキシブチル4.72質量部およびアクリル酸0.81質量部の混合液(b)100質量部を調製し、その60質量部を分取して、上記工程(1)により得られた共重合体(A)を含む溶液に添加して、第1の(メタ)アクリル酸エステル共重合体(A)の重合時に残留するモノマーとともに共重合させた。その後、溶液の一部についてGPCを用いて測定したところ、上記共重合体(A)の重量平均分子量18万のピークトップにほぼ変化がないことを確認するとともに、今回のGPC測定の結果から工程(1)におけるGPC測定の結果を差し引くことにより、新たに重量平均分子量1.5万の共重合体(B)の生成を確認した。ここで、共重合体(A)と共重合体(B)との配合比は、上記工程(1)における転化率が80%であったことから、32:68の質量比となる。
上記工程(2)により得られたアクリル系ポリマー溶液の固形分換算100質量部を分取し、メチルエチルケトンにて固形分濃度20質量%となるように希釈した。そして、イソシアネート系架橋剤(C)として、3.5質量部の1,6-ヘキサメチレンジイソシアネートのイソシアヌレート型3量体(日本ポリウレタン社製,商品名「コロネートHX」)を添加し、十分に撹拌することにより、粘着性組成物の希釈溶液を得た。
混合液(a)および(b)の組成を表1に記載されるように変更し、イソシアネート系架橋剤(C)、反応抑制剤、架橋促進剤および可塑剤を表2に記載されるように添加する以外、実施例1と同様にして粘着シートを製造した。
<測定条件>
・GPC測定装置:東ソー社製,HLC-8020
・GPCカラム(以下の順に通過):東ソー社製
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
・測定溶媒:テトラヒドロフラン
・測定温度:40℃
[アクリル酸エステル共重合体(A)および(B)]
2EHA:アクリル酸2-エチルヘキシル
BA:アクリル酸ブチル
4HBA:アクリル酸4-ヒドロキシブチル
AA:アクリル酸
EO(9mol):メトキシ基末端を有するポリエチレングリコール鎖(平均付加モル数=9モル)を含有するアクリル酸エステル
[イソシアネート系架橋剤(C)]
コロネートHX:1,6-ヘキサメチレンジイソシアネートのイソシアヌレート型3量体(日本ポリウレタン社製,商品名「コロネートHX」)
[架橋促進剤]
BXX3778-10(スズ化合物):ジブチルジラウリルスズ(東洋インキ製造社製,商品名「BXX3778-10」)
プキャット25(Bi化合物):ビスマス系金属有機化合物(日本化学産業製,商品名「プキャット25」,金属量として25質量%)
ZC-150(Zr化合物):ジルコニウムテトラアセチルアセトネート(マツモトファインケミカル社製,商品名「オルガチックスZC-150」)
実施例または比較例で得られた粘着シートから剥離シートを剥がし、露出した粘着剤層を、一方の面がケン化処理された厚さ80μmのトリアセチルセルロースフィルムのケン化処理面に貼合し、栗原製作所社製オートクレイブにて0.5MPa、50℃で、20分加圧した。その後、この積層体から、50mm幅、120mm長のサンプルを切り出した。
実施例または比較例にて作製した粘着性組成物の希釈溶液の粘度を、調製した直後、温度23℃および相対湿度50%の条件下に12時間放置した後、ならびに、同条件下に24時間放置した後において、B型粘度計(TOKIMEC社製,製品名:VISCOMETER)を用いて測定した。測定結果から、調製から12時間経過後の粘度の上昇率、および調製から24時間経過後の粘度の上昇率を算出した。これらの上昇率に基づいて、以下を基準にとしてポットライフを評価した。結果を表3に示す。
○:24時間後の上昇率が150%以内
△:12時間後の上昇率が150%以内
×:12時間後の上昇率が150%以上
11…粘着剤層
12…剥離シート
13…基材
Claims (12)
- 共重合体を構成するモノマー単位として、水酸基を有するモノマーおよびカルボキシル基を有するモノマーを含有する第1の(メタ)アクリル酸エステル共重合体(A)と、
前記第1の(メタ)アクリル酸エステル共重合体(A)の重量平均分子量よりも小さい重量平均分子量を有し、共重合体を構成するモノマー単位として、水酸基を有するモノマーおよびカルボキシル基を有するモノマーを含有する第2の(メタ)アクリル酸エステル共重合体(B)と、
イソシアネート系架橋剤(C)と
を含有する粘着性組成物であって、
前記第2の(メタ)アクリル酸エステル共重合体(B)を構成するモノマーにおける前記水酸基を有するモノマーの割合が、前記第1の(メタ)アクリル酸エステル共重合体(A)を構成するモノマーにおける前記水酸基を有するモノマーの割合よりも大きく、
前記第1の(メタ)アクリル酸エステル共重合体(A)および前記第2の(メタ)アクリル酸エステル共重合体(B)を構成するモノマーの質量部数の合計100質量部に対し、前記第1の(メタ)アクリル酸エステル共重合体(A)および前記第2の(メタ)アクリル酸エステル共重合体(B)を構成する前記カルボキシル基を有するモノマーの質量部数の合計が、0.1~1.0質量部であり、
前記第1の(メタ)アクリル酸エステル共重合体(A)と前記第2の(メタ)アクリル酸エステル共重合体(B)とにおける質量を基準とした配合比が、90:10~10:90である
ことを特徴とする粘着性組成物。 - 前記第1の(メタ)アクリル酸エステル共重合体(A)の重量平均分子量は、5万~50万であり、前記第2の(メタ)アクリル酸エステル共重合体(B)の重量平均分子量は、0.2万~10万であることを特徴とする請求項1に記載の粘着性組成物。
- 前記第1の(メタ)アクリル酸エステル共重合体(A)が、当該共重合体を構成するモノマー単位として、水酸基を有するモノマーを0.01~5質量%含有することを特徴とする請求項1または2に記載の粘着性組成物。
- 前記第2の(メタ)アクリル酸エステル共重合体(B)が、当該共重合体を構成するモノマー単位として、水酸基を有するモノマーを0.1~10質量%含有することを特徴とする請求項1~3の何れか一項に記載の粘着性組成物。
- 前記第2の(メタ)アクリル酸エステル共重合体(B)は、当該共重合体を構成するモノマー単位として、エチレンオキシドを含有することを特徴とする請求項1~4の何れか一項に記載の粘着性組成物。
- 前記粘着性組成物は、スズ化合物を含有しないことを特徴とする請求項1~5の何れか一項に記載の粘着性組成物。
- 請求項1~6に記載の粘着性組成物を製造する方法であって、
前記第1の(メタ)アクリル酸エステル共重合体(A)を構成するモノマーを、転化率50~90%でラジカル重合して、前記第1の(メタ)アクリル酸エステル共重合体(A)を製造する工程(1)と、
前記第1の(メタ)アクリル酸エステル共重合体(A)の重合時に残留するモノマーと、前記第2の(メタ)アクリル酸エステル共重合体(B)を構成するモノマーとを、前記第1の(メタ)アクリル酸エステル共重合体(A)の存在下でラジカル共重合して、前記第2の(メタ)アクリル酸エステル共重合体(B)を製造する工程(2)と、
前記イソシアネート系架橋剤(C)を添加する工程(3)と
を備えたことを特徴とする粘着性組成物の製造方法。 - 前記第2の(メタ)アクリル酸エステル共重合体(B)を製造する工程(2)において、前記第1の(メタ)アクリル酸エステル共重合体(A)の重合時に残留するモノマーと、前記第2の(メタ)アクリル酸エステル共重合体(B)を構成するモノマーとを、転化率70~100%でラジカル重合することを特徴とする請求項7に記載の粘着性組成物の製造方法。
- 請求項1~6のいずれかに記載の粘着性組成物を架橋してなる粘着剤。
- 基材と、粘着剤層とを備えた粘着シートであって、
前記粘着剤層が、請求項9に記載の粘着剤からなる
ことを特徴とする粘着シート。 - 前記粘着シートは、被着体を保護するための保護シートであることを特徴とする請求項10に記載の粘着シート。
- 前記被着体は、光学部材であることを特徴とする請求項11に記載の粘着シート。
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Cited By (5)
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JP2020045379A (ja) * | 2018-09-14 | 2020-03-26 | 日本カーバイド工業株式会社 | 偏光板用粘着剤組成物及び粘着剤層付偏光板 |
CN111171761A (zh) * | 2018-11-12 | 2020-05-19 | 藤森工业株式会社 | 粘着剂组合物及使用了该粘着剂组合物的粘着膜、表面保护膜 |
JP2022040328A (ja) * | 2020-11-19 | 2022-03-10 | 藤森工業株式会社 | 粘着剤組成物、粘着フィルム、表面保護フィルム及び粘着剤層付き光学フィルム |
JP7369073B2 (ja) | 2020-03-23 | 2023-10-25 | 日本カーバイド工業株式会社 | 光学部材保護フィルム用粘着剤組成物及び光学部材保護フィルム |
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RU207650U1 (ru) * | 2020-07-28 | 2021-11-09 | Святослав Владимирович Шевченко | Ременная передача |
RU205706U1 (ru) * | 2020-07-28 | 2021-07-29 | Святослав Владимирович Шевченко | Ременная передача |
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KR20190037137A (ko) * | 2017-09-28 | 2019-04-05 | 후지모리 고교 가부시키가이샤 | 점착제 조성물 및 표면 보호 필름 |
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CN111171761B (zh) * | 2018-11-12 | 2022-10-04 | 藤森工业株式会社 | 粘着剂组合物及使用了该粘着剂组合物的粘着膜、表面保护膜 |
CN111171761A (zh) * | 2018-11-12 | 2020-05-19 | 藤森工业株式会社 | 粘着剂组合物及使用了该粘着剂组合物的粘着膜、表面保护膜 |
JP7369073B2 (ja) | 2020-03-23 | 2023-10-25 | 日本カーバイド工業株式会社 | 光学部材保護フィルム用粘着剤組成物及び光学部材保護フィルム |
JP2022040328A (ja) * | 2020-11-19 | 2022-03-10 | 藤森工業株式会社 | 粘着剤組成物、粘着フィルム、表面保護フィルム及び粘着剤層付き光学フィルム |
JP7239751B2 (ja) | 2020-11-19 | 2023-03-14 | 藤森工業株式会社 | 粘着剤組成物、粘着フィルム、表面保護フィルム及び粘着剤層付き光学フィルム |
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TWI688627B (zh) | 2020-03-21 |
CN107109163A (zh) | 2017-08-29 |
JP6042592B6 (ja) | 2018-06-27 |
JP6042592B1 (ja) | 2016-12-14 |
JPWO2016147318A1 (ja) | 2017-04-27 |
TW201638277A (zh) | 2016-11-01 |
KR102271569B1 (ko) | 2021-07-02 |
CN107109163B (zh) | 2019-03-08 |
KR20170127402A (ko) | 2017-11-21 |
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