CN116023889A - Adhesive composition and adhesive layer - Google Patents
Adhesive composition and adhesive layer Download PDFInfo
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- CN116023889A CN116023889A CN202211317359.2A CN202211317359A CN116023889A CN 116023889 A CN116023889 A CN 116023889A CN 202211317359 A CN202211317359 A CN 202211317359A CN 116023889 A CN116023889 A CN 116023889A
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Abstract
Provided are an adhesive composition and an adhesive layer which are excellent in heat resistance and moist heat resistance, in addition to excellent initial high adhesion and re-peelability, and which maintain initial performance even after exposure to high temperature, high temperature and high humidity conditions. An adhesive composition comprising an acrylic polymer (A) and a crosslinking agent (B), wherein the acrylic polymer (A) has; the mass ratio (a 2/a 3) of the unit derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom to the unit derived from the (meth) acrylic monomer (a 3) containing a carboxyl group is 0.1 to 5.
Description
Technical Field
The present invention relates to an adhesive composition and an adhesive layer.
Background
Acrylic adhesives have been conventionally used in various fields such as double-sided tapes and printed labels. Among them, there are uses in which a curing tape used in a construction site, a label attached to a recycled container, or the like is attached to an adherend and then peeled off after a lapse of a certain period of time. The pressure-sensitive adhesive used in these applications is required to be cleanly releasable from the adherend without contaminating the adherend by the occurrence of residual glue on the surface of the adherend due to a part of the pressure-sensitive adhesive, that is, to be releasable.
In addition, the adhesive force required for the application is various, and it is required to design the adhesive in the range of all adhesive forces. In general, since the adhesive force increases with time after the adherend is attached, in particular, in the re-peeling application as described above, an initial adhesive force controlled to a certain degree of strength is required assuming that the adhesive force after the attachment increases. Therefore, there is a demand for a technology that exhibits a desired adhesive performance at the time of initial adhesion and also has a re-peelability that enables peeling of an adherend after a lapse of a certain period of time after the adhesion to the adherend without contaminating the adherend.
As such an adhesive, an adhesive comprising: a polymer obtained by solution polymerization of a monomer mixture containing 10 to 30 wt% of an alkyl (meth) acrylate having an alkyl group having 1 or 2 carbon atoms and a curing agent (for example, refer to patent document 1). However, although the pressure-sensitive adhesive has good removability, the pressure-sensitive adhesive has a problem that the initial pressure-sensitive adhesive is insufficient and cannot be applied to applications requiring high pressure-sensitive adhesive force.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2017-25200
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide an adhesive composition and an adhesive layer which are excellent in heat resistance and moist heat resistance, in addition to initial high adhesion and excellent in re-peelability, and which maintain initial performance even after exposure to high temperature and high humidity conditions.
Solution for solving the problem
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using an adhesive composition containing a specific acrylic polymer and a crosslinking agent, and have completed the present invention.
Specifically, the present invention relates to an adhesive composition comprising an acrylic polymer (a) and a crosslinking agent (B), wherein the acrylic polymer (a) has: the mass ratio (a 2/a 3) of the unit derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom to the unit derived from the (meth) acrylic monomer (a 3) containing a carboxyl group is 0.1 to 5.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive composition of the present invention can provide an adhesive layer having high adhesion, removability, heat resistance, and moist heat resistance, and therefore can be suitably used as an adhesive tape or sheet for use in label fixing, machine parts, electric parts, home appliance parts, OA equipment, labels, and the like.
Detailed Description
The adhesive composition of the present invention is an adhesive composition comprising an acrylic polymer (a) and a crosslinking agent (B), wherein the acrylic polymer (a) has: the mass ratio (a 2/a 3) of the unit derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom to the unit derived from the (meth) acrylic monomer (a 3) containing a carboxyl group is 0.1 to 5.
The acrylic polymer (a) has: units derived from an alkyl (meth) acrylate (a 1), a (meth) acrylic monomer (a 2) containing a nitrogen atom, and a (meth) acrylic monomer (a 3) having a carboxyl group.
The alkyl (meth) acrylate (a 1) includes an alkyl (meth) acrylate in which an alkyl group is bonded to an ester bond. The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 3 or more, further preferably 4 or more, preferably 20 or less, more preferably 15 or less, further preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl, and 2-ethylhexyl.
The alkyl (meth) acrylate (a 1) is preferably an alkyl acrylate.
As the alkyl (meth) acrylate (a 1), 1 or 2 or more kinds may be used, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and nonyl (meth) acrylate.
In the acrylic polymer (a), the content of the unit derived from the alkyl (meth) acrylate (a 1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, preferably 99% by mass or less, and still more preferably 90% by mass or less.
The (meth) acrylic monomer (a 2) having a nitrogen atom is a monomer having a nitrogen atom and a polymerizable double bond in the molecule, and preferably has an amide bond and a polymerizable double bond in the molecule, and examples thereof include a lactam compound having a vinyl group; a (meth) acrylamide monomer; a (meth) acrylate compound having a functional group containing a nitrogen atom (for example, an amino group, a 1-substituted amino group, a 2-substituted amino group, a nitrile group, or the like). These (meth) acrylic monomers (a 2) having a nitrogen atom may be used alone or in combination of 2 or more.
Examples of the lactam compound having a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam.
The (meth) acrylamide monomer is exemplified by (meth) acrylamideHaving hydrogen atoms or hydrocarbon radicals bound to the nitrogen atom (preferably aliphatic hydrocarbon radicals, where the hydrocarbon radicals contain-CH 2 -optionally substituted by-CO-the hydrogen atoms comprised in the hydrocarbon group being optionally substituted by hydroxy groups. ) And the like. In addition, in the case where 2 or more groups (the aforementioned hydrocarbon groups) are substituted on the nitrogen atom of (meth) acrylamide, these groups may be bonded to each other to form a ring containing a nitrogen atom.
The number of carbon atoms of the hydrocarbon group (preferably aliphatic hydrocarbon group) substituted on the nitrogen atom contained in the amide bond is preferably 1 or more, more preferably 10 or less, and still more preferably 6 or less.
As the (meth) acrylamide monomer, 1 or 2 or more kinds may be used. The (meth) acrylamide monomer may be any of (meth) acrylamide, an N-1 substituted (meth) acrylamide compound, and an N, N-2 substituted (meth) acrylamide compound.
As the (meth) acrylamide compound, 1 or 2 or more kinds may be used, and examples thereof include (meth) acrylamide; n-1 substituted (meth) acrylamide compounds such as N-isopropyl (meth) acrylamide, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N- (2-hydroxymethyl) acrylamide, and N- (2-hydroxyethyl) acrylamide; n- (meth) acryloylmorpholine, N- (meth) acryloylpiperidinone, N- (meth) acryloylpiperidines, N- (meth) acryloylpyrrolidines, N- (meth) acryloyl-4-piperidones, N-dimethyl (meth) acrylamides, N, N-2 substituted (meth) acrylamide compounds such as N-diethyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-methylenebis (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide.
Among them, the (meth) acrylamide monomer preferably contains a monomer represented by the formula (1).
[ type(1) Wherein R is 1 Represents a hydrogen atom or a methyl group. R is R 2 R is R 3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the-CH contained in the hydrocarbon group 2 -optionally substituted by-CO-or-O-, the hydrogen atoms contained in the hydrocarbon radical being optionally substituted by hydroxy groups, R 2 R is R 3 May be bonded to each other to form a ring containing a nitrogen atom.]
As the aforementioned R 2 R is R 3 The hydrocarbon group may be 1 or 2 or more, and examples thereof include a linear or branched saturated aliphatic hydrocarbon group; linear or branched unsaturated aliphatic hydrocarbon groups, and the like. Among them, a linear or branched saturated aliphatic hydrocarbon group is preferable, and a branched saturated aliphatic hydrocarbon group is more preferable. Preferably R 2 R is R 3 At least one of them is a hydrogen atom.
Among the units derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom, the content of the units derived from the (meth) acrylamide compound is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less.
Among the units derived from the aforementioned (meth) acrylic monomer (a 2) containing a nitrogen atom, the content of the units derived from the monomer represented by the formula (1) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less.
In the acrylic polymer (a), the content of the unit derived from the monomer (a 2) containing a nitrogen atom is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.
As the (meth) acrylic monomer (a 3) having a carboxyl group, 1 or 2 or more kinds may be used, and examples thereof include unsaturated monocarboxylic acids such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and β -carboxyethyl (meth) acrylate.
In the acrylic polymer (a), the content of the unit derived from the (meth) acrylic monomer (a 3) having a carboxyl group is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, preferably 20 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less.
In the acrylic polymer (a), the mass ratio (a 2/a 3) of the unit derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom to the unit derived from the (meth) acrylic monomer (a 3) having a carboxyl group is 0.1 to 5, preferably 0.2 to 3, more preferably 0.3 to 2.2, from the viewpoint of further improvement in heat resistance and moist heat resistance.
The acrylic monomer (a) may have a unit derived from a monomer (a 4) other than the alkyl (meth) acrylate (a 1), the (meth) acrylic monomer (a 2) containing a nitrogen atom, and the (meth) acrylic monomer (a 3) having a carboxyl group.
As the other monomer (a 4), 1 or 2 or more kinds may be used, and examples thereof include (meth) acrylic monomers having a hydroxyl group; epoxy ring-containing (meth) acrylic monomers such as glycidyl (meth) acrylate; alicyclic (meth) acrylic monomers such as cyclohexyl (meth) acrylate; aromatic vinyl monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylvinylbenzene, α -methylstyrene, p-methoxystyrene, p-t-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and p-hydroxystyrene; heterocyclic vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam and (meth) acryloylmorpholine; monomers having 2 or more vinyl groups, and the like.
Examples of the (meth) acrylic monomer having a hydroxyl group include compounds in which a hydroxyl group is bonded to an alkyl group of an alkyl (meth) acrylate; the polyalkylene glycol (meth) acrylate and the like are preferably compounds in which a hydroxyl group is bonded to an alkyl group of the alkyl (meth) acrylate, and more preferably compounds in which a hydroxyl group is bonded to a terminal of an alkyl group of the alkyl (meth) acrylate.
The number of hydroxyl groups contained in the (meth) acrylic monomer having a hydroxyl group is preferably 1. The (meth) acrylic monomer having a hydroxyl group is preferably an acrylic monomer having a hydroxyl group.
The alkyl acrylate may be the same as the alkyl (meth) acrylate (a 1).
As the (meth) acrylic monomer having a hydroxyl group, 1 or 2 or more kinds may be used, and examples thereof include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; polyethylene glycol (meth) acrylate, and the like.
In the acrylic polymer (a), the content of the unit derived from the (meth) acrylic monomer having a hydroxyl group is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less.
In the acrylic polymer (a), the content of the unit derived from the other monomer (a 4) is preferably 0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
The weight average molecular weight of the acrylic polymer (a) is preferably 10 ten thousand or more, more preferably 20 ten thousand or more, still more preferably 30 ten thousand or more, preferably 100 ten thousand or less, still more preferably 90 ten thousand or less, still more preferably 80 ten thousand or less.
In the present specification, the number average molecular weight and the weight average molecular weight of the acrylic polymer (a) represent converted values measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard sample.
In the pressure-sensitive adhesive composition of the present invention, the content of the acrylic polymer (a) in the nonvolatile component is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.
In the present specification, the nonvolatile component of the adhesive composition means a portion from which the solvent component contained in the adhesive composition as needed is removed.
The acrylic polymer (a) can be produced by copolymerizing the alkyl (meth) acrylate (a 1), the (meth) acrylic monomer (a 2) containing a nitrogen atom, the (meth) acrylic monomer (a 3) having a carboxyl group, and, if necessary, other monomers (a 4) in the presence of a polymerization initiator.
The polymerization initiator may be, for example, 1 or 2 or more kinds of thermal polymerization initiators, and examples thereof include peroxide initiators such as benzoyl peroxide and lauroyl peroxide, azo initiators such as azobisisobutyronitrile, and the like.
The adhesive composition of the present invention comprises a crosslinking agent (B). As the crosslinking agent, 1 or 2 or more kinds may be used, and examples thereof include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, polyvalent metal salt crosslinking agents, metal chelate crosslinking agents, ketohydrazide crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, silane crosslinking agents, glycidyl (alkoxy) epoxy silane crosslinking agents, and the like. Among them, isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, and glycidyl (alkoxy) epoxy silane crosslinking agents are preferable, isocyanate crosslinking agents, epoxy crosslinking agents, and carbodiimide crosslinking agents are more preferable, and isocyanate crosslinking agents are particularly preferable.
The content of the isocyanate crosslinking agent in the crosslinking agent (B) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less.
The content of the crosslinking agent (B) is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 7 parts by mass or less, based on 100 parts by mass of the acrylic polymer (a).
The adhesive composition of the present invention preferably contains a tackifying resin (C). The tackifier resin may be 1 or 2 or more kinds, and examples thereof include rosin-based resins such as unmodified rosin, modified rosin, and rosin derivatives; terpene resins such as unmodified terpenes, aromatic modified terpenes, hydrogenated terpenes and terpene phenols; polymeric resins such as petroleum resins, coumarone indene resins, and pure monomer (pure monomer) petroleum resins; a condensation resin such as a phenol resin and a xylene resin is preferable from the viewpoint of excellent compatibility with the acrylic polymer (a) and further excellent adhesion and excellent removability.
As the unmodified rosin, 1 or 2 or more kinds may be used, and examples thereof include gum rosin (gum rosin), wood rosin, tall oil rosin, and the like.
The modified rosin may be 1 or 2 or more, and examples thereof include disproportionated rosin, polymerized rosin, hydrogenated rosin, and the like.
As the rosin derivative, 1 or 2 or more kinds may be used, and examples thereof include rosin esters obtained by esterifying the unmodified rosin or the modified rosin; unsaturated fatty acid-modified rosin obtained by modifying the unmodified rosin or the modified rosin with an unsaturated fatty acid; an unsaturated fatty acid-modified rosin ester obtained by modifying the rosin ester with an unsaturated fatty acid; rosin alcohol obtained by reducing the carboxyl group contained in the unsaturated fatty acid-modified rosin or the unsaturated fatty acid-modified rosin ester; rosin metal salts such as unmodified rosin, modified rosin, rosin ester, unsaturated fatty acid-modified rosin ester, and rosin alcohol metal salt; rosin phenols, and the like.
As the above-mentioned unmodified terpene, 1 or 2 or more kinds may be used, and examples thereof include polymers of terpene compounds such as α -pinene, β -pinene, d-limonene, l-limonene, dipentene and the like.
As the aromatic modified terpene, 1 or 2 or more kinds may be used, and examples thereof include phenol modified products or styrene modified products of the unmodified terpenes.
As the terpene phenol, 1 or 2 or more kinds may be used, and examples thereof include resins obtained by copolymerizing a terpene and phenol.
The petroleum resin may be 1 or 2 or more, and examples thereof include aliphatic petroleum resins, aromatic petroleum resins, aliphatic/aromatic petroleum resins, and hydrides thereof.
As the tackifying resin (C), commercially available ones can be used, and examples of the rosin-based resins include PINECRYSTAL KR-85, KR-612 and KR-614 (above, manufactured by Kagaku chemical Co., ltd.); RONDIS R-CH, K-25, K-80, N-18 (manufactured by Sonchaka chemical Co., ltd.); white chrysanthemum Rosin (Shiragiku Rosin), ARDYME R-95, PINECRYSTAL KR-140 (manufactured by the above-mentioned Deskaching chemical industry Co., ltd.); HYPALE CH (manufactured by the above, described chemical industry, inc.); ester Gum AA-G, AA-L, AAV, 105, AT, pensel GA-100, AZ, PINECRYSTAL KE-359 (above, manufactured by Deskaching chemical Co., ltd.), HARIESTERTF, S, NEOTALL G2, HARITACK 8LJA, ER95 (above, harima Chemicals Group, manufactured by Inc.); ester Gum H, HP, PINECRYSTAL KE-311, PE-590 (manufactured by the above-described Kagaku Co., ltd.); PINECRYSTAL KE-100 (manufactured by Sonchaka chemical Co., ltd.); pensel C, D-125, D-135, D-160, KK, super Ester A-100, E-650, E-788, E-865NT (manufactured by Szechwan chemical Co., ltd., above), HARIESTER SK-323NS, SK-508H, SK-816E, SK-822E, HARITACK PCJ (manufactured by Inc., harima Chemicals Group, above); PINECRYSTAL KE-604 and KR-120 (from the above-mentioned Kagaku Kogyo Co., ltd.); TAMANOL E-100, E-200NT (manufactured by the above-mentioned Kagaku Co., ltd.); PINECRYSTAL KM-1500, KR-50M (above, manufactured by Kagaku Kogyo Co., ltd.), etc. Examples of the polymerizable resin include FTR0100, FTR2120, FTR2140, FTR6100, FTR6110, FTR6125, FTR7100, FTR8100, FTR8120, and FMR0150 (manufactured by san francisco, above).
In the pressure-sensitive adhesive composition of the present invention, the content of the tackifier resin (C) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, based on 100 parts by mass of the acrylic polymer (a).
The adhesive composition of the present invention preferably comprises a solvent (D). As the solvent (D), 1 or 2 or more kinds may be used, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; aliphatic hydrocarbon solvents such as hexane, and the like. Among them, an ester solvent is preferably contained.
The content of the ester solvent is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 100% by mass or less in the solvent (D).
The content of the solvent (D) in the adhesive composition is preferably 10 mass% or more, more preferably 30 mass% or more, still more preferably 50 mass% or more, preferably 90 mass% or less, more preferably 70 mass% or less, still more preferably 65 mass% or less.
The adhesive composition of the present invention may contain a base (ammonia water or the like), an acid for adjusting the pH; a foaming agent; a plasticizer; a softening agent; an antioxidant; fillers such as glass, plastic fibers, balloons, beads, and metal powders; colorants such as pigments and dyes; a pH regulator; a film formation auxiliary agent; a leveling agent; a thickener; a water repellent agent; a defoaming agent; an acid catalyst; acid generators and the like as additives.
The adhesive layer can be formed by applying the adhesive composition to a support and drying it. The support may be any of substrates such as a release sheet and an adhesive sheet.
As the coating method, a knife coater, a reverse coater, a die coater, a lip die coater (lip die coater), a slit coater, a gravure coater, a curtain coater, or the like can be used.
The thickness of the adhesive layer is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, preferably 100 μm or less, still more preferably 70 μm or less, still more preferably 50 μm or less.
The thickness of the base material is preferably 0.1 μm or more, and more preferably 1,000 μm or less.
Examples (example)
Hereinafter, the present invention will be described more specifically with reference to examples. The weight average molecular weight (Mw) was measured under the following GPC measurement conditions.
[ GPC measurement conditions ]
Measurement device: high performance GPC apparatus (HLC-8220 GPC manufactured by Tosoh Co., ltd.)
Column: the following columns manufactured by Tosoh corporation were used in series.
"TSKgel G5000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G4000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G3000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G2000" (7.8 mmI.D..times.30 cm). Times.1 root
A detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 0.4% by mass)
Standard sample: standard curves were made using standard polystyrene as described below.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-1 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-2 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-4 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-10 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-20 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-40 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-80 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-128 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-288 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-550 manufactured by Tosoh Co., ltd "
Synthesis example 1 Synthesis of acrylic Polymer (A-1)
To a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 930 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 29 parts by mass of acrylic acid, 20 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in with stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-1). The weight average molecular weight of the acrylic polymer (A-1) was 56 ten thousand.
Synthesis example 2 Synthesis of acrylic Polymer (A-2)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 950 parts by mass of n-butyl acrylate, 29 parts by mass of acrylic acid, 20 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in while stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-2). The weight average molecular weight of the acrylic polymer (A-2) was 65 ten thousand.
Synthesis example 3 Synthesis of acrylic Polymer (A-3)
To a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 930 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 19 parts by mass of acrylic acid, 30 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in with stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-3). The weight average molecular weight of the acrylic polymer (A-3) was 60 ten thousand.
Synthesis example 4 Synthesis of acrylic Polymer (A-4)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 910 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 19 parts by mass of acrylic acid, 50 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in with stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-4). The weight average molecular weight of the acrylic polymer (A-4) was 60 ten thousand.
Synthesis example 5 Synthesis of acrylic Polymer (A-5)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 920 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 29 parts by mass of acrylic acid, 30 parts by mass of diacetone acrylamide, 1 part by mass of hydroxyethyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in with stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-5). The weight average molecular weight of the acrylic polymer (A-5) was 55 ten thousand.
Synthesis example 6 Synthesis of acrylic Polymer (A-6)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 920 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 29 parts by mass of acrylic acid, 30 parts by mass of 2- (dimethylamino) ethyl methacrylate, 1 part by mass of hydroxyethyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in while stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-6). The weight average molecular weight of the acrylic polymer (A-6) was 55 ten thousand.
Synthesis example 7 Synthesis of acrylic Polymer (A-7)
To a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 630 parts by mass of n-butyl acrylate, 300 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl acrylate, 29 parts by mass of acrylic acid, 20 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in while stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (A-7). The weight average molecular weight of the acrylic polymer (A-7) was 65 ten thousand.
Synthesis example 8 Synthesis of acrylic Polymer (RA-1)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 950 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 29 parts by mass of acrylic acid, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in while stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. Thereafter, after being kept at 70℃for 8 hours under stirring, the content was cooled and filtered through a 200-mesh metal mesh to obtain a 40% by mass solution of the acrylic polymer (RA-1). The weight average molecular weight of the acrylic polymer (RA-1) was 50 ten thousand.
Synthesis example 9 Synthesis of acrylic Polymer (RA-2)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 945 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 29 parts by mass of acrylic acid, 5 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in with stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. Thereafter, after being kept at 70℃for 8 hours under stirring, the content was cooled and filtered through a 200-mesh metal mesh to obtain a 40% by mass solution of the acrylic polymer (RA-2). The weight average molecular weight of the acrylic polymer (RA-2) was 55 ten thousand.
Synthesis example 10 Synthesis of acrylic Polymer (RA-3)
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, and a thermometer, 814 parts by mass of n-butyl acrylate, 20 parts by mass of methyl acrylate, 15 parts by mass of acrylic acid, 150 parts by mass of dimethylacrylamide, 1 part by mass of 4-hydroxybutyl acrylate, and 1000 parts by mass of ethyl acetate were charged, and nitrogen gas was blown in with stirring, and the temperature was raised to 70 ℃. After 1 hour, 10 parts by mass (solid content: 5%) of a2, 2' -azobis (2-methylbutanenitrile) solution previously dissolved in ethyl acetate was added. After that, the content was cooled down after being kept at 70℃for 8 hours with stirring, and filtered through a 200-mesh metal mesh to obtain a 40 mass% solution of the acrylic polymer (RA-3). The weight average molecular weight of the acrylic polymer (RA-3) was 60 ten thousand.
TABLE 1
TABLE 2
Abbreviations in the tables are as follows.
BA: acrylic acid n-butyl ester
2EHA: 2-ethylhexyl acrylate
MA: acrylic acid methyl ester
DMAA: dimethylacrylamide
DAAM: diacetone acrylamide
DM: methacrylic acid 2- (dimethylamino) ethyl ester
AA: acrylic acid
4HBA: acrylic acid 4-hydroxybutyl ester
HEA: preparation of hydroxyethyl acrylate (example 1: preparation of adhesive composition (1))
To 100 parts by mass of the solution of the acrylic polymer (A-1) obtained in Synthesis example 1, 15 parts by mass of a tackifying resin (C-1; super Ester A-100 manufactured by Kagaku Co., ltd.) and 5 parts by mass of a tackifying resin (C-2; pensel D-135 manufactured by Kagaku Co., ltd.) were mixed with stirring, and 1.8 parts by mass of a crosslinking agent (B-1; FINETAC D-40 manufactured by DIC Co., ltd., a polyisocyanate-based crosslinking agent, and a solid content of 40% by mass) were homogenized, whereby an acrylic adhesive composition (1) was obtained.
( Examples 2 to 14: preparation of adhesive compositions (2) to (14) )
Acrylic pressure-sensitive adhesive compositions (2) to (14) were obtained in the same manner as in example 1 except that the type of the acrylic polymer (A-1) and the blending amount of the crosslinking agent (B-1) were changed as shown in tables 3 to 4.
( Comparative examples 1 to 6: preparation of adhesive compositions (R1) to (R6) )
Acrylic pressure-sensitive adhesive compositions (R1) to (R6) were obtained in the same manner as in example 1 except that the type of the acrylic polymer (A-1) and the blending amount of the crosslinking agent (B-1) were changed as shown in Table 5.
[ production of double-sided adhesive tape ]
The adhesive compositions obtained in examples and comparative examples were applied to the surface of a polyethylene terephthalate film (release PET 25) having a thickness of 25 μm, the surface of which was subjected to release treatment, so that the film thickness after solvent drying became 25 μm, and the solvent was evaporated in a dryer at 80 ℃ for 3 minutes, followed by bonding to a soft polyvinyl chloride substrate.
[ method for measuring adhesive force ]
The double-sided pressure-sensitive adhesive tape produced by the above method was cut into a width of 25mm with one side of PET25 μm bonded thereto, and the resultant was used as a test piece. The adherend was a stainless steel (BASUS) plate, an ABS plate, and a PP (polypropylene) plate, and was attached to the adherend with 2kg rolls×1 round trip. After 1 hour of adhesion, 180-degree peel strength was measured at 23℃under 50% RH atmosphere, and the resultant was used as adhesion.
[ method for measuring adhesion after moisture and heat resistance ]
The test piece was attached to the adherend in the same manner as in the method for measuring the adhesive force described above. Thereafter, the mixture was left at 60℃under a 90% RH atmosphere for 250 hours and taken out. After being left in an atmosphere of 50% RH at 23℃for 30 minutes, 180-degree peel strength was measured at a peeling rate of 300 mm/min as a heat-resistant adhesive strength.
[ method for measuring adhesion after heat resistance ]
The test piece was attached to the adherend in the same manner as in the method for measuring the adhesive force described above. Thereafter, the mixture was left in an atmosphere at 80℃for 250 hours and taken out. After being left in an atmosphere of 50% RH at 23℃for 30 minutes, 180-degree peel strength was measured at a peeling rate of 300 mm/min, and the resultant was used as a heat-resistant adhesive strength.
[ method of evaluating Repeaability ]
The test piece was attached to the adherend in the same manner as in the method for measuring the adhesive force described above. Thereafter, the mixture was left at 60℃under 90% RH atmosphere or 80℃atmosphere for 250 hours, and then taken out. After being left for 30 minutes in an atmosphere of 50% RH at 23 ℃, the test piece was peeled off, and the presence or absence of residual gum on the surface of the peeled adherend was confirmed as an evaluation of the re-peelability.
And (2) the following steps: residue-free adhesive
Delta: slightly residual adhesive
X: with adhesive residue
The evaluation results of examples 1 to 14 and comparative examples 1 to 6 are shown in tables 3 to 5.
TABLE 3
TABLE 4
TABLE 5
It was confirmed that the adhesive compositions of examples 1 to 14 produced an adhesive layer excellent in initial adhesion, heat resistance, wet heat resistance and re-peelability.
On the other hand, comparative examples 1 and 2 are examples in which the acrylic polymer (a) does not have a unit derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom, and it was confirmed that the re-peelability was insufficient.
Comparative examples 3 and 4 are examples in which the mass ratio (a 2/a 3) in the acrylic polymer (A) is less than the lower limit of 0.1 of the present invention, and it was confirmed that the re-peeling property after heat resistance was insufficient.
Comparative examples 5 and 6 are examples in which the mass ratio (a 2/a 3) in the acrylic polymer (A) is greater than the upper limit 5 of the present invention, and it was confirmed that the initial adhesion was insufficient.
Claims (5)
1. An adhesive composition comprising an acrylic polymer (a) and a crosslinking agent (B), wherein the acrylic polymer (a) has: the mass ratio (a 2/a 3) of the unit derived from the (meth) acrylic monomer (a 2) containing a nitrogen atom to the unit derived from the (meth) acrylic monomer (a 3) containing a carboxyl group is 0.1 to 5.
2. The adhesive composition according to claim 1, wherein the (meth) acrylic monomer (a 2) containing a nitrogen atom contains a (meth) acrylamide compound.
3. The adhesive composition according to claim 1 or 2, wherein the (meth) acrylic monomer (a 2) containing a nitrogen atom contains a monomer represented by formula (1),
in the formula (1), R 1 Represents a hydrogen atom or a methyl group, R 2 R is R 3 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the-CH contained in the hydrocarbon group 2 -optionally substituted by-CO-, the hydrogen atoms comprised in the hydrocarbon group being optionally substituted by hydroxy groups.
4. The adhesive composition according to any one of claims 1 to 3, further comprising a solvent (D).
5. An adhesive layer formed from the adhesive composition of any one of claims 1-4.
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