KR20160016589A - Adhesive composition, adhesive film, optical member and adhesive sheet - Google Patents
Adhesive composition, adhesive film, optical member and adhesive sheet Download PDFInfo
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- KR20160016589A KR20160016589A KR1020150092562A KR20150092562A KR20160016589A KR 20160016589 A KR20160016589 A KR 20160016589A KR 1020150092562 A KR1020150092562 A KR 1020150092562A KR 20150092562 A KR20150092562 A KR 20150092562A KR 20160016589 A KR20160016589 A KR 20160016589A
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- C09J7/0217—
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
Abstract
The pressure-sensitive adhesive film of the present invention comprises (A) a (meth) acrylic acid polymer, (B) a photopolymerization initiator and (C) a carbodiimide curing agent, (C) a carbodiimide-based curing agent, wherein the absolute value of the difference in gel fraction according to the following formula (1) is 10% or less:
[Formula 1]
Gel fraction difference = GF7-GF1
(GF7 and GF1 in the above formula 1 are as defined in the detailed description).
Description
The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive film, an optical member and a pressure-sensitive adhesive sheet.
2. Description of the Related Art In recent years, the use of flat-panel displays (FPD) such as liquid crystal displays (LCDs), plasma display panels (PDPs) and organic EL devices has been increasing. Accordingly, it is required to improve the workability and productivity of the pressure-sensitive adhesive used for the FPD and the like.
Patent Document 1 discloses a pressure-sensitive adhesive for a polarizing plate which is produced by irradiating actinic energy rays to an adhesive material comprising an acrylic copolymer and an active energy ray-curable compound. The pressure-sensitive adhesive composition for an optical film having the above structure has been disclosed to have excellent durability and light leakage property under high temperature and high temperature and high humidity conditions.
(Meth) acrylic acid ester polymer (A) containing a monomer having a nitrogen atom and an active energy ray-curable component (A) having a weight average molecular weight of 600,000 g / mol to 2,000,000 g / mol as a monomer unit constituting the polymer, (B) as a binder component. Also, unlike Patent Document 1, it is disclosed that the aging time from the irradiation of the active energy ray to the practical adhesive performance is about half a day, without using an isocyanate crosslinking agent. With such a constitution, the pressure-sensitive adhesive composition for an optical film has been disclosed to have excellent durability even under high temperature and high temperature and high humidity conditions.
However, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition described in Patent Document 1 requires a long aging time of 10 days from the irradiation of the active energy ray until the practical pressure-sensitive adhesive performance is reached, and the productivity is low . In addition, since an isocyanate-based crosslinking agent (isocyanate-based curing agent) is used in combination, the risk that the unreacted monomer in the isocyanate-based crosslinking agent gives to the respiratory system of the operator can not be ignored. In addition, since the pot life is short, problems have been left in terms of productivity.
Also, the pressure-sensitive adhesive composition described in Patent Document 2 employs an active energy ray curable compound having a structure (isocyanurate structure) containing isocyanurate in the form of a trimer of isocyanate, although an isocyanate crosslinking agent is not used in combination. Since the active energy ray curable compound having the isocyanurate structure has low reactivity with the (meth) acrylic acid-based polymer, about half a day is still required until the practical adhesive performance is reached after irradiation of the active energy ray .
It is an object of the present invention to provide an adhesive film and a pressure-sensitive adhesive composition which have a long pot life and excellent workability.
Another object of the present invention is to provide a pressure-sensitive adhesive film and a pressure-sensitive adhesive composition having excellent productivity by reaching practical adhesive performance in a shorter aging time.
Another object of the present invention is to provide a pressure-sensitive adhesive film and a pressure-sensitive adhesive composition which are excellent in leak resistance and durability.
It is still another object of the present invention to provide an optical member having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive film and the pressure-sensitive adhesive composition.
It is still another object of the present invention to provide a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive film and the pressure-sensitive adhesive composition.
DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies in order to solve the above problems and found that a pressure-sensitive adhesive film and a pressure-sensitive adhesive composition comprising a (meth) acrylic acid polymer, a photopolymerization initiator, a silane coupling agent and a carbodiimide-based curing agent having no isocyanate group The present inventors have found that the above problems can be solved and accomplished the present invention.
One aspect of the present invention relates to an adhesive film. In one embodiment, the adhesive film comprises (A) a (meth) acrylic acid polymer, (B) a photopolymerization initiator, and (C) a carbodiimide curing agent, wherein the absolute value of the gel fraction difference according to formula Or less.
[Formula 1]
Gel fraction difference = GF7-GF1
(GF7 in the above formula 1 is the gel fraction according to the following formula 2 after aging at 23 占 폚 and 45% relative humidity (RH) for 7 days after the activation energy ray irradiation treatment, and GF1 is 23 占 폚 And a gel fraction according to the following formula 2 after aging at 45% RH for 1 hour)
[Formula 2]
(In the above formula 2, W 1 is the weight of the test piece obtained after aging the adhesive film subjected to the activation energy ray irradiation treatment at 23 ° C and 45% RH for 1 hour or 7 days, W 2 is the weight of the 200 mesh wire , W 3 was obtained by aging the adhesive film, putting the specimen into a sample bottle, adding 30 g of ethyl acetate to the sample bottle, leaving at 25 ° C. for one day, and then drying the wire mesh and specimen at 90 ° C. for 1 hour And the weight of the wire mesh obtained).
In one embodiment, the adhesive film may have a gel fraction of 65% to 92% after 7 days of aging at 23 ° C and 45% RH after the active energy ray irradiation treatment.
In one embodiment, the adhesive film comprises (meth) acrylic acid polymer (A); A photopolymerization initiator (B); And a carbodiimide-based curing agent (C).
In one embodiment, the adhesive film comprises 100 parts by weight of the (meth) acrylic acid polymer (A); 0.05 to 4 parts by weight of a photopolymerization initiator (B); And 0.05 to 5 parts by weight of a carbodiimide-based curing agent (C).
In one embodiment, the carbodiimide-based curing agent (C) may be a carbodiimide-based curing agent containing no isocyanate group.
In one embodiment, the adhesive film may further comprise (D) a silane coupling agent.
In one embodiment, the adhesive film may include 0.05 to 0.5 parts by weight of the silane coupling agent (D) relative to 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, the adhesive film may further comprise 0 to 9 parts by weight of the (E) active energy ray curable compound per 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, the adhesive film may further comprise 1 to 8 parts by weight of (E) an active energy ray-curable compound per 100 parts by weight of the (meth) acrylate polymer (A).
In one embodiment, the photopolymerization initiator (B) and the active energy ray-curable compound (E) may be contained in a weight ratio of 1: 1 to 1:50.
In one embodiment, the photopolymerization initiator (B) and the carbodiimide-based curing agent (C) may be contained in a weight ratio of 1: 0.1 to 1:15.
In one embodiment, the adhesive film may further comprise 0.2 to 5 parts by weight of (F) an antistatic agent per 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, 90 parts by weight to 99.9 parts by weight of the (meth) acrylic acid ester monomer (a-1) and 100 parts by weight of the carboxyl group-containing monomer (a-2) And 0.1 to 10 parts by weight of at least one of the carboxyl group-containing (meth) acrylic monomer (a-3).
(A-1) 90 to 99.5 parts by weight of a (meth) acrylic acid ester monomer, 0.5 parts by weight of a carboxyl group-containing monomer (a-2), based on 100 parts by weight of the (meth) acrylic acid- (A-1), a carboxyl group-containing monomer (a-2) and a hydroxyl group-containing (meth) acrylic monomer. (Meth) acrylic monomer (a-3) may be 100 parts by weight.
In one embodiment, the adhesive force of the adhesive film may be 1 N / 25 mm to 6 N / 25 mm.
Another aspect of the present invention relates to a pressure-sensitive adhesive composition. In one embodiment, the pressure-sensitive adhesive composition comprises (A) 100 parts by weight of a (meth) acrylic acid-based polymer; (B) 0.05 to 4 parts by weight of a photopolymerization initiator; And (C) 0.05 to 5 parts by weight of a carbodiimide-based curing agent not containing an isocyanate group.
In one embodiment, the pressure-sensitive adhesive composition may further comprise 0.05 to 0.5 parts by weight of a silane coupling agent (D) based on 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, the pressure-sensitive adhesive composition may further include 0 to 9 parts by weight of (E) an active energy ray-curable compound per 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, 1 to 8 parts by weight of the active energy ray-curable compound (E) may be further added to 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, the photopolymerization initiator (B) and the active energy ray-curable compound (E) may be contained in a weight ratio of 1: 1 to 1:50.
In one embodiment, the photopolymerization initiator (B) and the carbodiimide-based curing agent (C) may be contained in a weight ratio of 1: 0.1 to 1:15.
In an embodiment, the structure of the active energy ray-curable compound (E) may be linear or branched.
In an embodiment, the pressure-sensitive adhesive composition may further comprise 0.2 to 5 parts by weight of (F) an antistatic agent per 100 parts by weight of the (meth) acrylic acid polymer (A).
In one embodiment, 90 parts by weight to 99.9 parts by weight of the (meth) acrylic acid ester monomer (a-1) and 100 parts by weight of the carboxyl group-containing monomer (a-2) (Meth) acrylic monomer (a-3) may be contained in an amount of 0.1 part by weight to 10 parts by weight.
(A-1) 90 to 99.5 parts by weight of a (meth) acrylic acid ester monomer, 0.5 parts by weight of a carboxyl group-containing monomer (a-2) And (a-3) hydroxyl group-containing (meth) acrylic monomer in a remaining amount.
In an embodiment, the (meth) acrylic acid polymer (A) may have a weight average molecular weight of 500,000 g / mol to 2,000,000 g / mol.
In an embodiment, the pressure-sensitive adhesive composition may have a viscosity of 300 mPa · s to 7000 mPa · s as measured at 25 ° C.
In an embodiment, the pressure-sensitive adhesive composition may have a gel fraction of 70% or more measured after 1 hour from the pressure-sensitive adhesive treatment.
In a specific example, the gel fraction after preservation for 7 days under the atmosphere of 23 캜 and 45% RH after the pressure-sensitive adhesive composition is 95% to 105% of the gel fraction after 1 hour from the pressure-sensitive adhesive composition.
Another aspect of the present invention relates to an optical member having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive film or the pressure-sensitive adhesive composition described above.
In an embodiment, the adhesive force of the pressure-sensitive adhesive layer may be 1 N / 25 mm to 6 N / 25 mm.
In an embodiment, the optical member may be formed by forming the pressure-sensitive adhesive film or the pressure-sensitive adhesive layer on a polarizing plate.
Another aspect of the present invention relates to a pressure-sensitive adhesive sheet comprising the above-mentioned pressure-sensitive adhesive film, or a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition.
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an adhesive film and a pressure-sensitive adhesive composition which are excellent in workability due to a long pot life, attain practical adhesive performance in a short aging time, and are excellent in productivity and excellent in light-resistance leakage resistance and durability.
Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. In the present specification, "(meth) acrylate" and "(meth) acrylic acid" are collectively referred to as "acrylate" and "methacrylate". Compounds containing (meta) such as " (meth) acrylic acid " are also collectively referred to as compounds having " meta "
In the present specification, " X to Y " representing the range means " X or more and Y or less ". Unless otherwise specified, the measurement of the operation and physical properties is carried out at room temperature (20 캜 to 25 캜) / relative humidity of 40% to 50%.
Adhesive film
One aspect of the present invention relates to an adhesive film. The adhesive film includes (A) a (meth) acrylic acid-based polymer, (B) a photopolymerization initiator, and (C) a carbodiimide-based curing agent. For example, the pressure-sensitive adhesive film may be formed of a pressure-sensitive adhesive composition comprising (A) a (meth) acrylic acid polymer, (B) a photopolymerization initiator, and (C) a carbodiimide-based curing agent.
The absolute value of the gel fraction difference according to the following formula 1 is 10% or less in the adhesive film:
[Formula 1]
Gel fraction difference = GF7-GF1
(GF7 in the above formula 1 is the gel fraction according to the following formula 2 after aging at 23 占 폚 and 45% relative humidity (RH) for 7 days after the activation energy ray irradiation treatment, and GF1 is 23 占 폚 And a gel fraction according to the following formula 2 after aging at 45% RH for 1 hour)
[Formula 2]
(In the above formula 2, W 1 is the weight of the test piece obtained after aging the adhesive film subjected to the activation energy ray irradiation treatment at 23 ° C and 45% RH for 1 hour or 7 days, W 2 is the weight of the 200 mesh wire , W 3 was obtained by aging the adhesive film, putting the specimen into a sample bottle, adding 30 g of ethyl acetate to the sample bottle, leaving at 25 ° C. for one day, and then drying the wire mesh and specimen at 90 ° C. for 1 hour And the weight of the wire mesh obtained).
When the gel fraction absolute value difference is as described above, practical sticking performance and stability can be excellent. For example, it may be 0% to 10%. Other examples may be 0% to 5%. Another example may be 0% to 3%.
In one embodiment, the adhesive film may have a gel fraction of 65% to 92% at the time of 7 days of aging at 23 ° C and 45% RH after the active energy ray irradiation treatment. When the gel fraction is in the above range, stable practical adhesive performance can be maintained over a long period of time and the stability can be excellent. For example from 69% to 88%.
In one embodiment, the thickness of the adhesive film (thickness after drying) may be 1 to 10 mm. Another example may be 5 [mu] m to 1.5 mm.
The active energy ray may be ultraviolet rays or electron rays. When the active energy ray is ultraviolet ray, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or the like can be used as a light source, and in the case of an electron ray, an electron beam accelerator or the like can be used as a light source.
The irradiation amount of the active energy ray in the active energy ray irradiation treatment may be 50 mJ / cm 2 to 1000 mJ / cm 2. It is possible to sufficiently generate the reaction of the ethylenic double bond contained in the component of the adhesive film in the above range and to obtain durability and desired adhesive properties when exposed to environmental changes, It is possible to perform the bridge without doing anything. For example, at an irradiation dose of 100 mJ / cm 2 to 700 mJ / cm 2. The irradiation can be performed at a dose of 120 mJ / cm 2 to 500 mJ / cm 2.
In the specific example, when the ultraviolet rays are irradiated to the pressure-sensitive adhesive composition using a metal halide lamp, irradiation can be performed at 500 mW / cm 2 to 2,000 mW / cm 2. The irradiation time may be set arbitrarily, but irradiation may be performed for 1 second to 10 seconds, for example. The atmosphere during the irradiation treatment is not particularly limited and may be carried out in air. However, it may be performed under an inert gas atmosphere such as nitrogen gas or argon gas from the viewpoint that the photo-curing can proceed without being influenced by oxygen in the air. The irradiation treatment may be performed at room temperature, or may be carried out on a stage heated to 40 to 80 캜.
In one embodiment, the adhesive film comprises (meth) acrylic acid polymer (A); A photopolymerization initiator (B); And a carbodiimide-based curing agent (C).
In one embodiment, the adhesive film comprises 100 parts by weight of the (meth) acrylic acid polymer (A); 0.05 to 4 parts by weight of a photopolymerization initiator (B); And 0.05 to 5 parts by weight of a carbodiimide-based curing agent (C).
In one embodiment, the carbodiimide-based curing agent (C) may be a carbodiimide-based curing agent containing no isocyanate group.
Pressure-sensitive adhesive composition
Another aspect of the present invention relates to a photocurable composition comprising 100 parts by weight of a (meth) acrylic acid polymer, 0.05 to 4 parts by weight of a photopolymerization initiator, 0.05 to 0.5 parts by weight of a silane coupling agent and 0.05 to 5 parts by weight of a carbodiimide- Sensitive adhesive composition. The pressure-sensitive adhesive composition having such a composition has a long pot life and excellent workability without using an active energy ray curable compound having an isocyanate crosslinking agent or an isocyanurate structure. In addition, in the conventional pressure-sensitive adhesive composition, about half a day of aging is required until the practical pressure-sensitive adhesive performance is attained. However, according to the present invention, the practical pressure-sensitive adhesive performance can be obtained even within 1 hour. The pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition according to the present invention is also excellent in light-leak resistance and durability.
Therefore, the pressure-sensitive adhesive composition of the present invention is effective for adhesion of various objects to be delivered, and thus the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive layer of an optical member or a pressure-sensitive adhesive sheet in particular.
(A) ( Meta ) Acrylic acid-based polymer
The pressure-sensitive adhesive film and the pressure-sensitive adhesive composition of the present invention comprise a (meth) acrylic acid-based polymer (in the present specification, the term "(meth) acrylic acid polymer (A)" or simply "component (A)").
As the (meth) acrylic acid-based polymer in the present invention, a polymer having a crosslinking point such as a carboxyl group, a hydroxyl group and an amino group is used. The (meth) acrylic acid-based polymer is not particularly limited, and can be appropriately selected from those conventionally used in the pressure-sensitive adhesive composition. Particularly, a (meth) acrylic acid-based polymer composed of at least one of the following (meth) acrylate monomer (a-1) and a carboxyl group-containing monomer (a- Can be used.
In one embodiment, 90 parts by weight to 99.9 parts by weight of the (meth) acrylic acid ester monomer (a-1) and 100 parts by weight of the carboxyl group-containing monomer (a-2) And 0.1 to 10 parts by weight of at least one of the carboxyl group-containing (meth) acrylic monomer (a-3).
In one embodiment, the (meth) acrylic acid polymer (A) comprises 90 to 99.5 parts by weight of the (meth) acrylic ester monomer (a-1), 0.5 to 10 parts by weight of the carboxyl group- (Meth) acrylate monomer (a-3), wherein the total amount of the (meth) acrylic acid ester monomer, the carboxyl group-containing monomer and the hydroxyl group-containing (meth) acrylic monomer is 100 wt% It is wealth.
The (meth) acrylic acid polymer (A) having the above composition suitably has a crosslinking point with a carbodiimide-based curing agent (C) to be described later. Therefore, foaming or light leakage of the pressure-sensitive adhesive layer due to excessively high degree of crosslinking can be prevented, and deterioration of the durability of the pressure-sensitive adhesive layer due to excessively low degree of crosslinking can be effectively prevented.
For example, the (meth) acrylic acid-based polymer (A) may contain 97 to 99.5 parts by weight of the (meth) acrylate monomer (a-1), 0.5 to 3 parts by weight of the carboxyl group- (Meth) acrylate monomer (a-3), wherein the total amount of the (meth) acrylic acid ester monomer, the carboxyl group-containing monomer, and the hydroxyl group-containing (meth) acrylic monomer is 100 Parts by weight).
(a-1) ( Meta ) Acrylic acid ester monomer
(Meth) acrylate ester monomer (also referred to as "(meth) acrylate monomer (a-1)" or simply "component (a-1)" in this specification) is a (meth) acrylate monomer having no hydroxy group in the molecule Acrylic acid. Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isobutyl (Meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobutyl (meth) acrylate, , 4-n-butyl cycl Acrylates such as hexyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxymethyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3- Butyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, phenoxy (Meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate , Trifluroethyl (meth) acrylate, pentadeca (Meth) acrylate, 2-chloroethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate and tribromophenyl Do not. These may be used alone or in combination of two or more.
For example, at least one of methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. Other examples include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) Rate may be used.
(a-2) a carboxyl group-containing monomer
The carboxyl group-containing monomer (also referred to as "carboxyl group-containing monomer (a-2)" or simply "component (a-2)" in the present specification) is an unsaturated monomer having at least one carboxyl group in the molecule. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric acid, crotonic acid, itaconic acid, itaconic anhydride, misteroolic acid, palmitoleic acid and oleic acid However, it is not altar. These may be used alone or in combination of two or more.
For example, at least one of (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, anhydrous fumaric acid, crotonic acid, itaconic acid and itaconic anhydride can be used. As another example, (meth) acrylic acid can be used.
(a-3) Hydroxyl group contain ( Meta ) Acrylic monomers
The hydroxyl group-containing (meth) acrylic monomer (also referred to as "hydroxyl group-containing (meth) acrylic monomer (a-3)" or simply "component (a-3)" in the present specification) Is an acrylic monomer bearing a group. Specific examples of hydroxyl group-containing (meth) acrylic monomers include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- N-2-hydroxyethyl (meth) acrylamide and cyclohexane dimethanol monoacrylate, and also alkyl glycidyl ether, aryl glycidyl (meth) acrylate, Acrylate, and glycidyl group-containing compounds such as glycidyl (meth) acrylate, and (meth) acrylic acid. These may be used alone or in combination of two or more.
For example, at least one of 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide and cyclohexane dimethanol monoacrylate . Other examples include at least one of 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and N-2-hydroxyethyl (meth) acrylamide.
Other Monomers
In addition to the components (a-1) to (a-3), other monomers copolymerizable therewith may also be used in the (meth) acrylic acid polymer (A) of the present invention. Acrylic monomers having an epoxy group such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; Amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate and methacryloxyethyltrimethylammonium chloride Ginny is an acrylic monomer; Acrylic monomers having an amide group such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N, N-methylene bis (meth) acrylamide; (Meth) acrylate having a phosphoric acid group such as 2-methacryloyloxyethyldiphenyl phosphate (meth) acrylate, trimethacryloyloxyethyl phosphate (meth) acrylate and triacryloyloxyethyl phosphate ; Acrylic monomers having a sulfonic acid group such as sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate and sodium 2-acrylamide-2-methylpropane sulfonate; Acrylic monomers having a urethane group such as urethane (meth) acrylate; acrylic vinyl monomers having a phenyl group such as p-tert-butylphenyl (meth) acrylate and o-biphenyl (meth) acrylate; Vinyltriethoxysilane, vinyltris (? -Methoxyethyl) silane, vinyltriacetylsilane, and methacryloyloxypropyltrimethoxysilane (? -Methoxyethylsilane), vinyltriacetoxysilane Vinyl monomers having a silane group; Styrene, chlorostyrene,? -Methylstyrene, vinyltoluene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, and vinyl pyridine. These other monomers may be used alone or in combination of two or more.
In an embodiment, the other monomer may be contained in an amount of 10% by weight or less based on the total weight of the (meth) acrylic acid polymer (A). When the content is within the above range, the adhesive property may be excellent. For example, 5% by weight or less. As another example, 0 to 5% by weight may be included.
(Meth) acrylic acid ester polymer (a-1) in an amount of 90 to 99.5 parts by weight, the carboxyl group-containing monomer (a-2) in an amount of 0.5 to 10 parts by weight, and (Meth) acrylate monomer (a-3), wherein the total amount of the (meth) acrylic acid ester monomer, the carboxyl group-containing monomer and the hydroxyl group-containing (meth) acrylic monomer is 100 wt% It is wealth. The (meth) acrylic acid polymer (A) having the above composition suitably has a crosslinking point with a carbodiimide-based curing agent (C) to be described later. Therefore, foaming or light leakage of the pressure-sensitive adhesive layer due to excessively high degree of crosslinking can be prevented, and deterioration of the durability of the pressure-sensitive adhesive layer due to excessively low degree of crosslinking can be effectively prevented.
For example, the (meth) acrylic acid-based polymer (A) may contain 97 to 99.5 parts by weight of the (meth) acrylate monomer (a-1), 0.5 to 3 parts by weight of the carboxyl group- (Meth) acrylate monomer (a-3), wherein the total amount of the (meth) acrylic acid ester monomer, the carboxyl group-containing monomer, and the hydroxyl group-containing (meth) acrylic monomer is 100 Parts by weight).
The method for producing the component (A) is not particularly limited, and conventionally known methods such as a method using a polymerization initiator, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, a thin film polymerization method, have. Examples of the polymerization control method include an adiabatic polymerization method, a temperature control polymerization method, and an isothermal polymerization method. In addition to the method of initiating polymerization by a polymerization initiator, a method of initiating polymerization by irradiation with radiation, electron beams, ultraviolet rays, or the like may be employed. For example, a solution polymerization method using a polymerization initiator can be used because the molecular weight can be easily controlled and the amount of impurities can be reduced. As specific examples, ethyl acetate, toluene, methyl ethyl ketone and the like can be used.
For example, by adding 0.01 to 0.50 parts by weight of a polymerization initiator to 100 parts by weight of the total amount of the monomers and reacting the mixture at a reaction temperature of 60 캜 to 90 캜 for 3 hours to 10 hours under a nitrogen atmosphere. Examples of the polymerization initiator in the specific examples include azo compounds such as azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile) and azobiscyanovaleric acid; tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethyl hexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert- Organic peroxides such as roper oxide; Inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate. These may be used alone or in combination of two or more.
The weight average molecular weight (Mw) of the component (A) may be 500,000 g / mol to 2,000,000 g / mol. For example from 1,000,000 g / mol to 1,800,000 g / mol. Other examples may be 1,200,000 g / mol to 1,600,000 g / mol. When the weight average molecular weight is 500,000 g / mol or more, durability is enhanced. On the other hand, when the weight average molecular weight is 2,000,000 g / mol or less, the bonding property is improved. In the present invention, the polystyrene reduced value measured by the gel permeation chromatography described in Examples is adopted as the weight average molecular weight.
The component (A) may be used alone or in combination of two or more.
(B) Photopolymerization initiator
The pressure-sensitive adhesive film and the pressure-sensitive adhesive composition of the present invention include a photopolymerization initiator (also referred to herein as a "photopolymerization initiator (B)" or simply "component (B)"). The photopolymerization initiator contained in the pressure-sensitive adhesive composition generates radicals in the light irradiation process for a pressure-sensitive adhesive composition described later, and enhances the reactivity of the ethylenic double bond of the (meth) acrylic acid polymer or the active energy ray curable compound described below. By including the photopolymerization initiator in the pressure-sensitive adhesive composition, practical adhesive performance can be obtained in a short aging time. Although not intending to limit the technical scope of the present invention, it is believed that the pressure-sensitive adhesive composition comprising a photopolymerization initiator is faster in polymerization rate as compared with the thermosetting pressure-sensitive adhesive composition using an isocyanate-based curing agent or the like.
In an embodiment, the photopolymerization initiator includes 4-phenoxy dichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyl trichloroacetophenone, diethoxyacetophenone, 2-hydroxy- Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- (2-hydroxy-2-propyl) ketone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl diisopropyl ether, benzyl diisopropyl ether, Methyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-methyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbo ) Benzophenone, 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2,1,2-bimidazole, 2,2- Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylphenylglyoxylate, benzyl, 9- Acetophenone-based compounds such as 10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethyl anthraquinone and 2-isopropylthioxanone, benzoin compounds, benzophenone compounds, triazine compounds, Based compounds and the like can be used alone or in combination of two or more.
The photopolymerization initiator may be synthesized or a commercial product may be used. Examples of commercially available photopolymerization initiators include Irgacure (registered trademark) 369, Irgacure (registered trademark) 784, Irgacure (registered trademark) 651, Irgacure (registered trademark) 184, Irgacure (registered trademark) 500 (Registered trademark) series such as Irgacure (registered trademark) 1000, Irgacure (registered trademark) 149, Irgacure (registered trademark) 819, Irgacure (registered trademark) 261, (Registered trademark) 1173 manufactured by BASF Japan Co., Ltd. and the like (manufactured by BASF Japan Co., Ltd.).
The component (B) is contained in an amount of 0.05 to 4 parts by weight (solid content ratio) based on 100 parts by weight of the component (A). When the amount of the component (B) is less than 0.05 part by weight, the crosslinking does not sufficiently proceed even after the activation energy irradiation treatment by UV irradiation or the like. When the component (B) is contained in an amount exceeding 4 parts by weight, the crosslinking proceeds excessively, so that the stress of the pressure-sensitive adhesive layer is lowered, the polarizer can not follow the contraction of the polarizer during high temperature storage, light leakage occurs, Can be degraded. For example, 0.1 to 3.5 parts by weight (solid content ratio). For example, 0.5 to 3 parts by weight (solid content ratio).
(C) Carbodiimide system Hardener
The pressure-sensitive adhesive film and the pressure-sensitive adhesive composition of the present invention include a carbodiimide-based curing agent having no isocyanate group (in this specification, "carbodiimide-based curing agent (C)" or simply "component (C)"). The isocyanate group is a group represented by -N = C = O. Conventionally, an isocyanate-based curing agent was often used in the pressure-sensitive adhesive composition, but since the crosslinking reaction by the isocyanate-based curing agent was activated by heat, the progress was slow and it took a long time for the aging time. In addition, unreacted monomers have the risk of adversely affecting the health of workers. In the present invention, by using a carbodiimide-based curing agent, not only the aging time is shortened but also an advantage from the viewpoint of safety. Further, when the pressure-sensitive adhesive composition is used for a polarizing plate, adhesion of the pressure-sensitive adhesive layer and the polarizing plate can be improved by using a carbodiimide-based curing agent.
Further, in consideration of the shortening of the pot life of the pressure-sensitive adhesive composition and the safety of the operator, the pressure-sensitive adhesive composition of the present invention may not contain an isocyanate-based curing agent.
Among the carbodiimide-based curing agents, there is also an isocyanate group represented by the following formula (1) (for example, Kabodite (registered trademark) V-01 (Nisshinbo Chemical Co., Ltd.)):
[Chemical Formula 1]
When a carbodiimide-based curing agent having an isocyanate group is used in the pressure-sensitive adhesive composition, the pot life is shortened. It is considered that this is because the crosslinking reaction progresses gradually even at room temperature like the isocyanate-based curing agent. On the other hand, in the present invention, by using a carbodiimide-based curing agent having no isocyanate group, the pot life is long and workability is excellent. The technical scope of the present invention is not limited, but it is considered that this is because the crosslinking reaction does not proceed until the activation energy irradiation treatment is performed by UV irradiation or the like.
The carbodiimide-based curing agent (C) used in the present invention is not particularly limited and includes, for example, a compound (polycarbodiimide) having two or more carbodiimide groups (-N═C═N-) Can be used. Or it is possible to use a known polycarbodiimide.
In the present specification, the term "carbodiimide-based curing agent having no isocyanate group" means that the NCO content (%) expressed by the weight fraction of the isocyanate group present in the carbodiimide-based curing agent is substantially 0%. Concretely, a carbodiimide type curing agent having an NCO content of less than 0.5% measured according to JIS K1603-1 (2007) is used.
The component (C) may be synthesized or a commercial product may be used. (NCO content: 0%), carbodite (registered trademark) V-09 (NCO content: 0%) (not less than 2%), and the like. Examples of commercial products of carbodiimide type curing agents having no isocyanate group include carboditol V- , Nisshinbo Chemical Co., Ltd.), and the like.
The component (C) is contained in an amount of 0.05 to 5 parts by weight (solid content ratio) based on 100 parts by weight of the component (A). When the amount of the component (C) is less than 0.05 part by weight, the adhesiveness of the adhesive layer to the base material is lowered, the staining property of the object to be delivered increases and the reworkability is lowered. Or the like, it may become a cause of lowering the production yield of optical members and the like. When the amount of the component (C) exceeds 5 parts by weight, crosslinking proceeds excessively, so that light leakage and durability are reduced. For example, the component (C) may include 0.07 part by weight to 4 parts by weight (solid content ratio). Other examples include 0.1 to 2.8 parts by weight (solids content). The component (C) may be used alone or in combination of two or more.
(D) Silane coupling agent
The pressure-sensitive adhesive film and pressure-sensitive adhesive composition of the present invention may further comprise a silane coupling agent (also referred to herein as a "silane coupling agent (D)" or simply "component (D)"). By using a silane coupling agent, the mechanical strength of the pressure-sensitive adhesive layer is improved, and a pressure-sensitive adhesive layer having excellent durability can be obtained.
Specific examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n -Butyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinyltriclorosilane, Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane, 3-glycidoxypropylmethyldiethoxysilane,? - (3,4-epoxycyclohexyl) Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyl (Aminoethyl) -? - aminopropylmethyldimethoxysilane, N -? - (amino (meth) acryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane, Aminopropyltrimethoxysilane,? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane, Phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane and bis- (3- (triethoxy Silyl) propyl) tetrasulfide, and the like.
A silane coupling agent having a functional group such as an epoxy group (glycidoxy group), an amino group, a mercapto group and a (meth) acryloyl group, a silane coupling agent containing a functional group having reactivity with these functional groups, , And a compound having a hydrolyzable silyl group obtained by reacting each functional group at an arbitrary ratio can also be used.
In the present invention, a silane coupling agent alkoxy oligomer (silane coupling agent oligomer) may be used as the silane coupling agent. The silane coupling agent alkoxy oligomer is a silane coupling agent having at least two silane compounds having an alkoxy group condensed to form a -Si-O-Si- structure, at least one alkoxy group bonded to the silicon atom, ≪ / RTI > The above-mentioned silane coupling agent alkoxy oligomer has an alkoxy group, so that adhesion to glass used for a liquid crystal panel or the like is developed. Further, by having an organic functional group, the silane coupling agent alkoxy oligomer is excellent in compatibility with the (meth) acrylic acid-based polymer, and can exhibit a so-called anchor effect in the (meth) acrylic acid-based polymer . However, the present invention is not limited by these considerations.
Examples of the organic functional group of the silane coupling agent alkoxy oligomer include a vinyl group, an epoxy group, a styryl group, a (meth) acryloyl group, a methacryloxy group, an acryloxy group, an amino group, an ureido group, a chloropropyl group, a mercapto group and a polysulfide group And the like. For example, an epoxy group, a mercapto group, a (meth) acryloyl group, and the like may be added in order to achieve both improvement in durability and realization of low adhesive property of the resulting pressure-sensitive adhesive layer. Other examples may have an epoxy group and a mercapto group.
Since the silane coupling agent oligomer is a dendrimer having two silicon atoms in one molecule, the number of silicon atoms per molecule can be up to about 100, that is, an average degree of polymerization of 2 to 100 can be used. When the average degree of polymerization is increased, the viscosity of the silane coupling agent oligomer becomes high, which may result in a paste form or a solid form, which makes handling difficult. For example, the average polymerization degree may be 2 to 80. [ Other examples may be from 3 to 50.
The organic functional group contained in the silane coupling agent oligomer is usually bonded to a silicon atom via a suitable linking group. Examples of the linking group include divalent hydrocarbon groups such as methylene, ethylene, trimethylene, hexamethylene and decamethylene groups, aromatic rings such as methylphenylethyl, methoxymethyl, methoxy A divalent aliphatic group having an oxygen atom in between, such as an ethyl group or a methoxypropyl group. When the organic functional group in the sphere is an epoxy group, a functional group may be formed between two neighboring carbon atoms constituting the ring.
The silane coupling agent oligomer is not particularly limited, and examples thereof include homopolymers and copolymers of the above-mentioned silane compounds.
The silane coupling agent may be synthesized or a commercially available product may be used. Examples of commercially available silane coupling agents include Shinetsu Silicone (registered trademark) KBM-303, KBM-403, KBE-402, KBM-403, X-41-1805 (a silane coupling agent oligomer having a mercapto group, a methoxy group and an ethoxy group), X-41-1810 (a silane coupling group having a mercapto group, a methyl group and a methoxy group), KBM- X-41-1053 (a silane coupling agent oligomer having an epoxy group, a methoxy group and an ethoxy group), X-41-1058 (a silane coupling agent oligomer having an epoxy group, a methyl group and a methoxy group) Ltd.) and the like.
KBM-403, KBM-5103, KBM-573, KBM-802, KBM-803, KBE-846, X-41-1805 and KBM- X-41-1810 or the like can be used. Other examples of the silane coupling agent include KBM-403 and X-41-1810. The silane coupling agents may be used alone or in combination of two or more.
The component (D) may be contained in an amount of 0.05 part by weight to 0.5 part by weight (solid content ratio) based on 100 parts by weight of the component (A). When included in the above range, the pressure-sensitive adhesive layer of the present invention can be excellent in durability and resistance to light leakage. For example, the component (D) may include 0.07 part by weight to 0.45 part by weight (solid content ratio). For example, 0.1 to 0.3 parts by weight (solid content ratio).
(E) active Energy line Curable compound
The pressure-sensitive adhesive film and pressure-sensitive adhesive composition of the present invention may further comprise an active energy ray-curable compound (referred to as "active energy ray curable compound (E)" or simply "component (E)" in this specification). The pressure-sensitive adhesive composition of the present invention contains an unreacted ethylenic double bond derived from the (meth) acrylic acid polymer (A) even when it does not contain the active energy ray curable compound, Can be given. However, since the pressure-sensitive adhesive composition includes the active energy ray-curable compound, the abundance of the ethylenic double bond in the pressure-sensitive adhesive composition that is activated by the photopolymerization initiator (B) is stable, have. Further, since the pressure-sensitive adhesive composition contains the active energy ray curable compound, the gel fraction after the activation energy ray irradiation treatment is improved.
The active energy ray-curable compound of the present invention can use a multifunctional (meth) acrylate-based monomer. Examples of such multifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (Meth) acrylate (n = 4 to 20), ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6- (Meta) acrylate, pentaerythritol tri (meth) acrylate, trimethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (Meth) acrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, Acryloyloxypropyl methacrylate, and tris (2- (meth) acryloyloxyethyl) isocyanurate, and the like. For example.
The component (E) may be synthesized or a commercial product may be used. In a specific example, the commercial product is NK ester such as NK ester A-HD-N, NK ester A-TMPT, NK ester AD-TMPT, NK ester APG-100, NK ester A- DPH, NK ester A- A, light acrylate 9EG-A, light acrylate 14EG-A, light acrylate NP-A, light acrylate MPG-A, light acrylate 9EG-A, (Registered trademark) series (manufactured by Toagosei Co., Ltd.) such as a light acrylate series (Kyoeisha Kagaku Co., Ltd.) such as M-220, M-225, M-240, M-309, M- ) Can be used.
The active energy ray curable compound used in the present invention may not have an isocyanurate structure. The isocyanurate structure refers to a structure represented by the following formula (2), which is formed by the trimerization reaction of isocyanate:
(2)
By using an active energy ray curable compound having no isocyanurate structure, pot life can be increased. For example, the presence of the isocyanurate structure can be analyzed by means such as by measuring the carbonyl 1,690cm -1 to 1,700cm -1 of isocyanurate structure in the FT-IR. In the present invention, the active energy ray curable compound having a linear or branched chain structure can be used.
The component (E) may be contained in an amount of 0 to 9 parts by weight (solid content ratio) based on 100 parts by weight of the component (A). When the content is within the above range, the gel fraction after the active energy ray irradiation treatment is improved, excessive crosslinking proceeds, and light leakage or durability can be prevented from being lowered. For example, 1 part by weight to 8 parts by weight (solid content ratio). For example, 1.5 to 7 parts by weight (solid content ratio).
The component (E) may be used alone or in combination of two or more.
In one embodiment, the photopolymerization initiator (B) may be contained in a weight ratio of 1: 0.1 to 1:15 with the carbodiimide-based curing agent (C). When the adhesive layer is formed as described above, the surface resistance value is low, and the adhesion and the workability can be excellent. Specifically, the photopolymerization initiator (B) may be contained in a weight ratio of 1: 0.1 to 1: 0.5 with the carbodiimide-based curing agent (C).
In another embodiment, the photopolymerization initiator (B) and the active energy ray-curable compound (E) may be contained in a weight ratio of 1: 1 to 1:50. When the weight ratio is included, the durability and the light-leak resistance of the adhesive layer can be excellent. For example, in a weight ratio of 1: 1 to 1:10.
(F) Antistatic agent
The pressure-sensitive adhesive film and pressure-sensitive adhesive composition of the present invention may further comprise an antistatic agent (also referred to as " antistatic agent (F) " or simply " component (F) " When the pressure-sensitive adhesive composition contains an antistatic agent, the surface resistance value of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is lowered. This makes it possible to effectively suppress the generation of the static electricity when it becomes necessary to peel off the liquid crystal cell or the like due to bonding mist or the like. As a result, it is possible to stably prevent the dust from being easily adhered to the surface of the polarizing plate or the like, the disturbance easily occurs in the liquid crystal alignment, or the electrostatic breakdown of the peripheral circuit element tends to occur easily.
As the antistatic agent that can be used in the present invention, an ion conductive agent such as an ionic liquid, a surfactant, and the like are suitably used.
In an embodiment, the ionic liquid includes at least one selected from the group consisting of a phosphonium ion, a pyridinium ion, a pyrrolidinium ion, an imidazolium ion, a guanidinium ion, an ammonium ion, an isonium ion, a thioronium ion, A cyanide ion, a quaternary ammonium ion and a quaternary phosphonium ion and a cation component such as a halide ion, a nitrate ion, a sulfate ion, a phosphate ion, a perchlorate ion, a thiocyanate ion, a thiosulfate ion, , A tetrafluoroborate ion, a hexafluorophosphate ion, a formate ion, an oxalate ion, an acetic acid ion, a trifluoroacetic acid ion, and an alkylsulfonic acid ion. More specifically, there may be mentioned 1-allyl-3-methylimidazolium chloride, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium dimethylphosphate, Ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium iodide, 1-ethyl-3-methanesulfonate, Methyl-imidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium chloride, 1-hexyl 1-methyl-1-propyl-pyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-methylpyrrolidinium bromide, Methylpiperidinium bromide, 1-ethylpyridinium chloride, 1-ethylpyridinium bromide, 1-butylpyridinium chloride, 1-butylpyridinium bromide Butyl-3-methylpyridinium chloride, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium hexafluorophosphate, (Trifluoromethanesulfonyl) imide, tetrabutylammonium chloride, tetrabutylammonium bromide, cyclohexyltrimethylammonium bis (triphenylmethanesulfonyl) imide, triphenylmethylammonium bis (trifluoromethanesulfonyl) imide, Fluoromethanesulfonyl) imide, tetrabutylphosphonium bromide, and the like.
For example, bis (fluorosulfonyl) imide salts represented by the following formula (3) may be used as the ionic conductor:
(3)
In Formula 3, A is a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms; X is any one of a cation selected from the group consisting of hydrogen, an alkali metal, an alkaline earth metal, ammonium, phosphonium, alkylammonium, and alkylphosphonium. For example, A is a fluorine atom and X is H + , Li + , Na +, or K + .
The surfactant may be a nonionic surfactant or an ionic surfactant. In a specific example, the nonionic surfactant is a fluorinated surfactant such as a fluoroaliphatic polymer ester (for example, FC-4430, FC-4432 or 3M), a polyethylene glycol alkyl ether, a polyoxyalkyl And alkyl ethers. In an embodiment, the nonionic surfactant may be a cationic surfactant such as a C 8 to C 22 alkyl trimethylammonium halide, or an anionic surfactant such as an alkyl sulfate.
In an embodiment, the component (F) may include 0.2 parts by weight to 5 parts by weight (solid content ratio) based on 100 parts by weight of the component (A). For example, 0.8 to 2.5 parts by weight (solid content ratio).
The component (F) may be used alone or in combination of two or more.
Other ingredients
The pressure-sensitive adhesive film and the pressure-sensitive adhesive composition of the present invention can be used in combination with a curing accelerator, a lithium salt, an inorganic filler, a softening agent, an antioxidant, an antioxidant, a stabilizer, a tackifier resin, a modified resin (polyol resin, phenol resin, (Coloring pigments, extender pigments, etc.), treating agents, ultraviolet light blocking agents, fluorescent whitening agents, dispersing agents, heat stabilizers, antioxidants, Light stabilizers, ultraviolet absorbers, lubricants and solvents.
Specific examples of the curing accelerator include dibutyltin dilaurate, JCS-50 (manufactured by Joho Kakaku Corp.) and FOMATE (registered trademark) TK-1 (manufactured by Mitsui Chemicals, Inc.).
In an embodiment, the antioxidant is selected from dibutylhydroxytoluene (BHT), Irganox (registered trademark) 1010, Irganox (registered trademark) 1035FF and Irganox (registered trademark) 565 .
In the specific examples, the tackifier resin includes rosin such as rosin acid, polymerized rosin acid and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin and petroleum resin.
When the additive is used, for example, the additive may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the component (A), but is not particularly limited.
Manufacturing method
The pressure-sensitive adhesive composition of the present invention may be prepared by mixing the components described above at one time, sequentially mixing the components, mixing the components with each other, mixing the remaining components, and stirring can do. More specifically, it can be prepared by stirring at room temperature or, if necessary, heating (for example, at a temperature of 30 to 40 캜) until it becomes homogeneous in a stirrer or the like. For example, stirring for 5 minutes to 5 hours.
The viscosity of the pressure-sensitive adhesive composition of the present invention is not particularly limited. However, considering easiness of coating, ease of control of the thickness of the pressure-sensitive adhesive layer formed from the composition, and the like, it is preferable to measure by a B-type viscometer immediately after compounding at 25 캜 (within 10 minutes after mixing each component for a predetermined time) One viscosity may be from 300 mPa s to 7000 mPa s. For example, when used as a pressure-sensitive adhesive for an optical member, the viscosity at 25 占 폚 immediately after preparation (within 10 minutes from mixing each component for a predetermined time) may be 1000 mPa 占 퐏 to 6000 mPa 占 퐏. Other examples may be from 2500 mPa · s to 5000 mPa · s.
The pot life can be evaluated by comparing the viscosity of the composition immediately after the pressure-sensitive adhesive composition is blended with the viscosity of the composition after 12 hours from preparation (blending). The composition that has not been gelled can be used as the composition after 12 hours from blending. When the viscosity of the composition immediately after the pressure-sensitive adhesive composition is blended (the composition solution in the case of the solution) is taken as 100%, the viscosity of the composition after 12 hours from the blending (in the case of solution, the composition solution) . And can be a pressure-sensitive adhesive composition having excellent workability in the above range. For example, within 110%. The pressure-sensitive adhesive composition of the present invention has an excellent pot life because the excess viscosity or gelation of the pressure-sensitive adhesive composition is suppressed after preparation of the composition.
In the present specification, the term "immediately after" means within 10 minutes. That is, the "viscosity of the composition immediately after the preparation of the pressure-sensitive adhesive composition" means the viscosity measured within 10 minutes after completion of preparation of the pressure-sensitive adhesive composition (mixing the components for a predetermined time).
The pressure-
The pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention is formed of a coating film of the pressure-sensitive adhesive composition as described above, and the pressure-sensitive adhesive layer is imparted with tackiness by irradiation with active energy.
Since the pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator, radicals are generated by performing an activation energy irradiation treatment and photopolymerization is carried out by the growth reaction of the ethylenic double bond of the (meth) acrylic acid polymer or the active energy ray curable compound. As a result, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention reaches the practical pressure-sensitive adhesive performance in a short period of time after the pressure-sensitive adhesive process (after the activation energy irradiation process) is within one hour.
The pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention is obtained by applying the pressure-sensitive adhesive composition as described above between a release film and a substrate, and includes those before and after crosslinking. The optical member or pressure-sensitive adhesive sheet on which the pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition before crosslinking is formed may be subjected to activation energy irradiation treatment in use to give pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) with tackiness.
The curing of the pressure-sensitive adhesive composition of the present invention is generally performed after the pressure-sensitive adhesive composition is applied to the substrate, but it is also possible to transfer the pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition after crosslinking to the substrate. Further, the above-mentioned pressure-sensitive adhesive composition may be coated on the release film, and after drying the coating film of the pressure-sensitive adhesive composition as required, the base material may be laminated on the coating film.
Alternatively, a separate release film (second release film) having a different peeling force may be laminated on the coating film by applying the pressure-sensitive adhesive composition on the release film, drying the coating film of the pressure-sensitive adhesive composition if necessary. According to this aspect, not only the pressure-sensitive adhesive composition can be transported but also the photo-curing can be performed without being influenced by oxygen in the air due to the production of the pressure-sensitive adhesive composition and the use of such pressure- You can proceed. In addition, by setting a predetermined difference in the peeling force between the two peeling films, it is possible to prevent the peeling film from partially following the peeling film when the peeling film having a lower peeling force is peeled off.
For example, the release film is obtained by applying a release agent such as silicone resin to a polyester film such as polyethylene terephthalate (PET), polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene to form a release layer . In an embodiment, the release film may have a thickness within a range of 20 to 150 mu m.
In the specific examples, the base material may include, but not limited to, a polarizing plate, a polarizing layer protective film, a viewing angle enlarging film, an antiglare film, a retardation plate, and an optical film usable in a liquid crystal display. In particular, in the case of the pressure-sensitive adhesive composition of the present invention, the occurrence of light leakage can be effectively suppressed even when the substrate is a polarizing plate. According to an embodiment of the present invention, there is provided an optical member in which a pressure-sensitive adhesive layer is formed on a polarizing plate. Further, since the pressure-sensitive adhesive composition of the present invention can adhere durability to a polarizer well, the polarizer itself produced by stretching an iodine-containing polyvinyl alcohol resin as a raw material of a polarizing plate can also be used as a substrate. A polarizer in which one side of the polarizer is coated with a protective film such as triacetyl cellulose or polyethylene terephthalate is also applicable.
In an embodiment, the material of the substrate is selected from the group consisting of polyvinyl alcohol, polyethylene terephthalate, triacetyl cellulose, polycarbonate, liquid crystal polymer, cycloolefin, polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, poly Ether ether ketone, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, alicyclic structure-containing polymer, and aromatic polymer.
The substrate may be subjected to a surface treatment. Examples of such surface treatment include primer treatment, corona treatment, and flame treatment. For example corona treatment. The adhesion of the pressure-sensitive adhesive layer to the base film can be further improved when the surface-treated base material is applied.
The method of applying the pressure-sensitive adhesive composition is not particularly limited. For example, a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method and the like can be used. If necessary, a pressure-sensitive adhesive composition to which a solvent is added may be applied to form a coating film, followed by drying. The drying conditions may be generally within a range of from 50 ° C to 150 ° C for 10 seconds to 10 minutes. Examples of the solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, ethyl isobutyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. In the embodiment, when the solvent is added, the concentration of the pressure-sensitive adhesive composition may be in the range of 5 wt% to 30 wt%.
The coating thickness (thickness after drying) of the pressure-sensitive adhesive composition when used in the optical member can be selected according to the substrate and the application to be used. For example, from 1 mu m to 100 mu m. For example, 5 [mu] m to 50 [mu] m.
The coating film of the pressure-sensitive adhesive composition prepared as described above is subjected to active energy ray irradiation treatment to form a pressure-sensitive adhesive layer. For example, the active energy ray may be ultraviolet ray or electron ray. When the active energy ray is ultraviolet ray, a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, or the like can be used as a light source, and in the case of an electron ray, an electron beam accelerator or the like can be used as a light source.
When the coating film of the pressure-sensitive adhesive composition is formed on the release film, the irradiation of the active energy ray can be performed from the side of the release film. This makes it possible to efficiently perform irradiation without damaging the substrate such as the polarizing plate.
The irradiation amount of the active energy ray in the active energy ray irradiation treatment may be 50 mJ / cm 2 to 1000 mJ / cm 2. It is possible to sufficiently generate the reaction of the ethylenic double bonds in the component (A) and the component (E) in the above range, and to obtain durability and desired pressure-sensitive adhesive properties when exposed to environmental changes, Or crosslinking can be carried out without destroying the substrate. For example, at an irradiation dose of 100 mJ / cm 2 to 700 mJ / cm 2. The irradiation can be performed at a dose of 120 mJ / cm 2 to 500 mJ / cm 2.
In the specific example, when the ultraviolet rays are irradiated to the pressure-sensitive adhesive composition using a metal halide lamp, irradiation can be performed at 500 mW / cm 2 to 2,000 mW / cm 2. The irradiation time may be set arbitrarily, but irradiation may be performed for 1 second to 10 seconds, for example. The atmosphere during the irradiation treatment is not particularly limited and may be carried out in air. However, it may be performed under an inert gas atmosphere such as nitrogen gas or argon gas from the viewpoint that the photo-curing can proceed without being influenced by oxygen in the air. The irradiation treatment may be performed at room temperature, or may be carried out on a stage heated to 40 to 80 캜.
Optical member And a pressure-
The present invention provides an optical member and a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive film or pressure-sensitive adhesive composition of the present invention.
Optical member
Examples of the optical member in the specific examples include a polarizing plate, a retarder, an optical film for a flat display, and a conductive film for a touch panel. Among them, the pressure-sensitive adhesive composition of the present invention is excellent in adhesion between the polarizing plate and glass. Needless to say, the present invention is not limited to the above-described embodiment, but can be used for bonding other members. According to an embodiment of the present invention, there is provided an optical member in which the pressure-sensitive adhesive layer is formed on a polarizing plate.
The pressure-sensitive adhesive composition of the present invention may be used by forming a pressure-sensitive adhesive layer directly on one side or both sides of an optical member, or by previously forming a pressure-sensitive adhesive layer on the release film and transferring the pressure- .
The pressure-sensitive adhesive composition of the present invention exhibits excellent flexibility, so that it can follow the shrinkage of the polarizing plate with a lapse of time in particular when used for a polarizing plate, and excellent light-leak resistance can be obtained. Further, since the pressure-sensitive adhesive composition of the present invention has excellent durability, lifting and peeling of the pressure-sensitive adhesive layer by heat treatment and high-humidity treatment can be prevented.
When the pressure-sensitive adhesive composition of the present invention is used in an optical member, the gel fraction of the pressure-sensitive adhesive layer after 1 hour from the pressure-sensitive adhesive working (active energy ray irradiation treatment) may be 65% to 92%. As the optical member having the pressure-sensitive adhesive layer in the above-mentioned range, punching or slitting can be performed quickly. For example from 70% to 90%. The gel fraction of the pressure-sensitive adhesive layer after 7 days of storage under the atmosphere of 23 ° C and 45% RH after the pressure-sensitive adhesive processing can be 95% to 105%, assuming that the gel fraction after one hour from the pressure-sensitive adhesive processing is 100%. Such a pressure-sensitive adhesive layer has stable practical sticking performance over a long period of time and is excellent in stability. In order to set the gel fraction as described above, the conditions may be appropriately selected, for example, the addition amount of each component is adjusted within the above range. For example from 97% to 103%.
In the optical member of the present invention, the adhesive force of the pressure-sensitive adhesive film or pressure-sensitive adhesive layer formed on the optical member may be 1 to 6 (N / 25 mm). If the adhesive strength is in this range, the reworkability can be advantageous. For example, 2 to 5 (N / 25 mm). In the present specification, the " adhesive force " is determined by measuring according to the adhesive tape adhesive sheet test method of JIS Z0237 (2000), and more specifically, by the method described in the following examples.
The pressure-sensitive adhesive composition of the present invention used in the optical member has a long pot life and is excellent in workability. The aging time after the pressure-sensitive adhesive process reaches within 1 hour and reaches practical adhesive performance in a short time, and productivity is greatly improved. The pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive film or the pressure-sensitive adhesive composition of the present invention used for the optical member has not only excellent light-leak resistance but also an appropriate adhesive force for an optical member and adhesion to a substrate, , And excellent workability.
Adhesive sheet
The pressure-sensitive adhesive composition of the present invention can be applied to a substrate or a separator and dried (crosslinked) to form a pressure-sensitive adhesive layer, thereby forming a pressure-sensitive adhesive sheet such as a sheet or tape. That is, the present invention provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive film or pressure-sensitive adhesive composition of the present invention.
As the base material of the pressure-sensitive adhesive sheet, various known thin-film members such as foams of rubber, paper, and aluminum foil are used in addition to those described above. The surface of these substrates may be subjected to a treatment such as corona treatment, plasma treatment, formation of an easy-to-adhere layer, formation of an antistatic layer, and the like depending on the material thereof. As the separator, various kinds of plastic films, such as the above-described plastic film having the surface treated with a peeling treatment such as silicon, fluorine or long chain alkyl, or a polypropylene film not subjected to such a peeling treatment can be used .
When a pressure-sensitive adhesive film layer or a pressure-sensitive adhesive layer is formed on a substrate, the pressure-sensitive adhesive film layer or the pressure-sensitive adhesive layer may be formed on one surface thereof to form a single-sided pressure-sensitive adhesive sheet. When the pressure-sensitive adhesive composition is formed on both sides, the pressure-sensitive adhesive composition of the present invention may be applied to only one side of the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive paper may be formed on both sides of the pressure-sensitive adhesive paper. When the pressure-sensitive adhesive layer is formed on the separator, it can be used as a double-sided pressure-sensitive adhesive sheet.
When the pressure-sensitive adhesive composition of the present invention is used in a pressure-sensitive adhesive sheet, the gel fraction of the pressure-sensitive adhesive layer after 7 days from the activation energy ray irradiation treatment may be from 65% to 92%. As the adhesive sheet having the pressure-sensitive adhesive layer in the above-mentioned range, punching or slitting can be performed quickly. For example from 70% to 90%. The gel fraction of the pressure-sensitive adhesive layer after 7 days of storage under the atmosphere of 23 ° C and 45% RH after the pressure-sensitive adhesive processing can be 95% to 105%, assuming that the gel fraction after one hour from the pressure-sensitive adhesive processing is 100%. Such a pressure-sensitive adhesive layer has stable practical sticking performance over a long period of time and is excellent in stability. In order to set the gel fraction as described above, the conditions may be appropriately selected, for example, the addition amount of each component is adjusted to the above range. For example from 97% to 103%.
In the pressure-sensitive adhesive sheet of the present invention, the adhesive force of the pressure-sensitive adhesive film or the pressure-sensitive adhesive layer formed on the pressure-sensitive adhesive sheet may be 0.05 to 20 (N / 25 mm). If the adhesive strength is in this range, it is possible to cope with a pressure-sensitive adhesive sheet such as a sheet or a tape in which various adhesive forces are required. For example, 0.1 to 10 (N / 25 mm).
Example
The effects of the present invention will be described with reference to the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments. The solid content and viscosity of the (meth) acrylic acid polymer solution obtained in Synthesis Example, the viscosity of the pressure-sensitive adhesive composition solution and the weight average molecular weight of the component (A) were measured by the following methods.
<Solid content>
About 1 g of the (meth) acrylic acid-based polymer solution was precisely weighed into a precisely weighed glass plate. After drying at 105 DEG C for 1 hour, the temperature was returned to room temperature, and the total weight of the glass plate and the remaining solid content was precisely weighed. The solid content was calculated by the following formula (3) by taking the total weight of the glass plate and the (meth) acrylic acid-based polymer solution before drying and the weight of the glass plate as Y, and the total weight of the glass plate and the remaining solid content as Z .
[Formula 3]
<Viscosity>
The (meth) acrylic acid-based polymer solution put in a glass bottle was temperature-adjusted to 25 캜 and measured by a B-type viscometer. The viscosity of the pressure-sensitive adhesive composition solution was measured immediately after the pressure-sensitive adhesive composition solution was blended and twice after 12 hours from blending.
≪ Weight average molecular weight &
The weight average molecular weight was measured according to the measurement method and measurement conditions shown in Table 1 below.
(Synthesis Example 1)
To a flask equipped with a reflux condenser and a stirrer, 99 parts by weight of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 1 part by weight of 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) And 120 parts by weight of ethyl were added. Subsequently, the mixture was heated to 65 DEG C while nitrogen substitution was carried out, and 0.04 part by weight of azobisisobutyronitrile (AIBN) was added. Polymerization was carried out at 65 DEG C for 6 hours. After completion of the polymerization reaction, 280 parts by weight of ethyl acetate was added and diluted to obtain a solution of a (meth) acrylic acid polymer (Sample Name: A-1). The obtained (meth) acrylic acid-based polymer solution had a solid content of 20% by weight and a viscosity of 4500 mPa 占 퐏. The (meth) acrylic acid polymer (A-1) thus obtained had a weight average molecular weight of 1,600,000 g / mol.
(Synthesis Examples 2 to 11)
(Meth) acrylic acid type polymers (A-2) to ((A-2)) were obtained in the same manner as in Synthesis Example 1, except that the composition of the monomer components in Synthesis Example 1 was changed to the compositions shown in Table 2 A-11) was obtained. The solids content and viscosity of the resulting (meth) acrylic acid polymer (A-2) to (A-11) solution and the weight average molecular weight of the (meth) acrylic acid polymer Respectively. The results are shown in Table 2 below. Also in the following Table 2, " BA " is butyl acrylate; &Quot; MA " is methyl acrylate; &Quot; HEA " is 2-hydroxyethyl acrylate; &Quot; 4HBA " is 4-hydroxybutyl acrylate; &Quot; HEAA " is N-2-hydroxyethyl acrylamide; &Quot; AA " is acrylic acid.
BA: butyl acrylate (manufactured by Nihon Shokubai Co., Ltd.)
MA: methyl acrylate (manufactured by Nihon Shokubai Co., Ltd.)
MEA: methoxyethyl acrylate (manufactured by Nihon Shokubai Co., Ltd.)
HEA: 2-hydroxyethyl acrylate (manufactured by Nihon Shokubai Co., Ltd.)
4HBA: 4-hydroxybutyl acrylate (manufactured by Nippon Kayaku Co., Ltd.)
HEAA: hydroxyethylacrylamide (manufactured by Kojin Film & Chemicals Co., Ltd.)
AA: Acrylic acid (manufactured by Nippon Shokubai Co., Ltd.)
(Example 1)
500 parts by weight of the (meth) acrylic acid polymer solution obtained in the above Synthesis Example 1 (100 parts by weight as solid content of the (meth) acrylic acid polymer (A)), Irgacure (registered trademark) 500 2 parts by weight of a silane coupling agent (D), Shin-Etsu Silicone (registered trademark) KBM (trade name, manufactured by BASF Japan KK), 2 parts by weight of 1-hydroxy-cyclohexylphenylketone: benzophenone = 1: , 0.1 part by weight of a carbodiimide-based curing agent (C) having no isocyanate group, 0.1 part by weight of a polyoxyalkylene-polyoxyalkylene group -403 (3- glycidoxypropylmethyldiethoxysilane, product of Shin-Etsu Chemical Co., ), 2 parts by weight of V-09 (product of Nisshinbo Chemical Co., Ltd., sample name C-1) and NK ester A-TMPT (trimethylolpropane triacrylate, product of Shin Nakamura Co, 4 parts by weight of a pressure-sensitive adhesive composition (components (A) to (E) The concentration of total) subjected to ethyl acetate to 17% by weight, and mixed for 10 minutes at room temperature (25 ℃), to obtain a solution (pressure-sensitive adhesive composition solution), with a pressure-sensitive adhesive composition is dissolved.
This solution was coated on a peelable PET film (MRF38, thickness: 38 mu m, manufactured by Mitsubishi Resin Co., Ltd.) so as to have a thickness of 25 mu m after drying in a Baker applicator, Followed by drying for a minute to form a pressure-sensitive adhesive layer. Thereafter, a polarizing plate or a separate peeling film (second peeling film) having a different peeling force was laminated to obtain a polarizing plate or a pressure-sensitive adhesive sheet on which a pressure-sensitive adhesive layer was formed.
The active energy ray irradiation treatment was performed on the pressure-sensitive adhesive layer formed on the polarizing plate or between the release films under the following conditions. The active energy ray irradiation treatment was performed within 3 minutes from the above lamination.
Equipment used: AIG GRANDEJI ECS-401GX (manufactured by iGraphics Co., Ltd.)
Light source: metal halide lamp
Irradiation dose: 1000 mJ / cm 2
Conveyor speed: 5m / min.
(Examples 2 to 11 and Comparative Examples 1 to 3)
(Meth) acrylic acid polymer, a photopolymerization initiator, a silane coupling agent, a carbodiimide curing agent, an active energy ray curable compound, an antistatic agent, and other additives synthesized in the above Synthesis Example were used , A solution in which the pressure-sensitive adhesive composition was dissolved was prepared, and a polarizing plate or pressure-sensitive adhesive sheet with a pressure-sensitive adhesive layer was produced. The photopolymerization initiators B-1 and B-2, the carbodiimide-based curing agents C-1 and c-2, the silane coupling agents D-1 and D-2, the active energy ray curable compounds E-1 to E- The details of the inhibitors F-1 to F-2 and other additives G are as follows. The weight parts in Table 3 are not the addition amounts of the respective products but the addition amounts of the active ingredients.
B-1: 1-Hydroxy-cyclohexyl phenyl ketone: benzophenone = 1: 1 (w / w)
(Irgacure (registered trademark) 500 manufactured by BASF Japan Co., Ltd.)
B-2: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
(Irgacure (registered trademark) 819, product of BASF Japan Co., Ltd.)
C-1: Kabodite (registered trademark) V-09GB (manufactured by Nisshinbo Chemical Co., Ltd.)
c-2: Kabodite (registered trademark) V-01 (manufactured by Nisshinbo Chemical Co., Ltd.)
D-1: 3-glycidoxypropylmethyldiethoxysilane
(Shin-Etsu Silicone (registered trademark) KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
D-2: Shin-Etsu Silicone (registered trademark) X-41-1810 (Shin-Etsu Kagakukogyo Co., Ltd.)
E-1: Trimethylolpropane triacrylate (NK Ester A-TMPT, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)
E-2: Dipentaerythritol hexaacrylate (NK Ester A-DPH, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)
E-3: Triethylene glycol diacrylate (Light Acrylate 3EG-A, manufactured by Koeishakagaku Co., Ltd.)
E-4: Trimethylolpropane trimethacrylate (NK Ester TMPT, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)
F-1: 1-Butyl-4-methylpyridinium hexafluorophosphate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
F-2: Tributylmethylammonium bis (trifluoromethanesulfonyl) imide (manufactured by Toko Seiko Kogyo Co., Ltd.)
G: Trimethylol propane / tolylene diisocyanate
(Coronate (registered trademark) L manufactured by Nippon Polyurethane Coating Co., Ltd.)
Among the above carbodiimide-based curing agents, D-1 (carboditel V-09) does not have an isocyanate group (NCO content: 0% 01) has an isocyanate group (NCO content: 9.8%). As shown in Formula 4, the active energy ray curable compounds E-1 to E-4 have a linear or branched chain structure.
[Chemical Formula 4]
In order to evaluate the practical adhesive performance of the pressure-sensitive adhesive layer, the performance of the polarizing plate or pressure-sensitive adhesive sheet on which the pressure-sensitive adhesive layer according to Examples and Comparative Examples was formed was evaluated according to the following methods. In the following evaluation, " within 1 hour after the production " means providing to the test within 1 hour after the active energy ray irradiation treatment.
(1) Gel fraction
Using the pressure-sensitive adhesive sheets prepared in Examples 1 to 11 and Comparative Examples 1 to 3, the gel fraction of the pressure-sensitive adhesive composition was measured. The gel fraction was determined by the following method. That is, after the active energy ray irradiation treatment, the pressure-sensitive adhesive sheet was stored in an atmosphere of 23 ° C and 45% RH. After 5 minutes, 1 hour and 7 days after the active energy ray irradiation treatment, about 0.1 g of the pressure-sensitive adhesive composition was weighed and the weight W 1 (g) was measured. This was taken in a sample bottle, about 30 g of ethyl acetate was added, and the mixture was allowed to stand for 24 hours. The predetermined time and the contents of the sample bottle wire mesh of 200 mesh after the lapse of a total of (the weight of the networks W 2 (g)) was filtered away from the, wire mesh, and the residue was dried for 1 hour at 90 ℃ weight W 3 (g) Respectively. The gel fraction was calculated from these measured values by the following equation (2).
[Formula 2]
(2) Metal corrosion inhibition and prevention
Within one hour after the polarizing plate having the pressure-sensitive adhesive layer was formed, the pressure-sensitive adhesive layer surface was bonded to the aluminum foil. Thereafter, it was stored under an atmosphere of 60 DEG C and 95% RH. On the 2nd and 10th days of storage, the corrosion was observed. In Table 3, " o " indicates no change and " x " indicates whitened.
(3) Leakage resistance property
Immediately after the polarizing plate with the pressure-sensitive adhesive layer was prepared, the polarizing plate was cut to 120 mm (polarizing plate MD (machine direction)) × 60 mm and 120 mm (polarizing plate TD (transverse direction) × 60 mm) And the autoclave treatment was performed for 20 minutes under the conditions of 50 占 폚 and 0.49 MPa (5 kg / cm2). Thereafter, the sample was stored under an atmosphere of 85 캜, and appearance was observed for 120 hours and 500 hours from the start of storage. In Table 3, "? &Quot; indicates that no light leakage was observed after 120 hours and 500 hours, " Good " indicates that light leakage was not observed after 120 hours, " And " x " indicates that light leakage was observed, respectively.
(4) Durability
Immediately after the polarizing plate with the pressure-sensitive adhesive layer was prepared, the polarizing plate was cut to 120 mm (polarizing plate MD direction) x 60 mm and attached to an alkali-free glass (Eagle XG manufactured by Corning Incorporated) Cm < 2 >) for 20 minutes. Thereafter, the appearance was observed for 500 hours in an atmosphere of 85 캜 and an atmosphere of 60 캜 and 95% RH. Furthermore, a heat shock test was performed in which two cycles of -40 ° C for 30 minutes (first stage) and 85 ° C for 30 minutes (second stage) were repeated for one cycle for 200 cycles, and the appearance after the test was observed. In Table 3, " o " indicates that no foaming, lifting and peeling were observed, " DELTA " indicates peeling observed at a portion of the end, and " x " indicates that at least one of foaming, Respectively.
(5) Adhesion
Immediately after the polarizing plate with the pressure-sensitive adhesive layer was prepared, the polarizing plate was cut into a width of 25 mm and attached to an alkali-free glass (Eagle XG, product of Corning Incorporated) under the conditions of 50 캜 and 0.49 MPa (5 kg / And autoclave treatment was carried out. The adhesive strength was measured in accordance with the adhesive tape and pressure-sensitive adhesive sheet test method described in JIS Z0237 (2000) at a peel angle of 180 ° and a peel rate of 0.3 m / min under an atmosphere of 23 ° C and 45% RH using a tensile tester Respectively.
(6) Adhesion to substrate
5. The adhesiveness was observed when the adhesion was measured. In Table 3, " o " indicates that the pressure-sensitive adhesive was not peeled off from the substrate at all, and " x "
(7) Pollution of adherend
The contact angle of the glass plate surface before and after the above (5) adhesion measurement was measured. The measurement of the contact angle was carried out in accordance with the wettability test method of the substrate glass surface described in JIS R3257 (1999). In Table 3, " o " indicates that the change in the contact angle of the glass plate surface before and after the adhesion measurement is 3 DEG or less, and " x " indicates that the contact angle change of the glass plate surface before and after the adhesion measurement exceeds 3 DEG.
(8) Surface resistance value
Immediately after the polarizing plate with the pressure-sensitive adhesive layer was prepared, the surface resistance of the pressure-sensitive adhesive layer side of the polarizing plate was measured using a resistivity meter Hirestor UP (manufactured by Mitsubishi Kagaku) under an atmosphere of 23 ° C and 45% RH. The applied voltage was set to 100V.
(9) Re-workability
5. The peeling state was observed when the adhesion was measured. In Table 3, " o " indicates that interfacial destruction was observed, and " x " indicates that the pressure-sensitive adhesive was electrodeposited and / or cohesive failure was observed on a glass plate (object to be delivered).
Referring to Table 3, the pressure-sensitive adhesive compositions (Examples 1 to 11) of the present invention had a pot life that was longer than that of the pressure-sensitive adhesive compositions (Comparative Examples 1 to 3) It was found that the practical sticking performance was reached even in the case of aging. It was also found that the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention (Examples 1 to 11) was excellent in light-leak resistance and durability.
Claims (28)
Wherein the absolute value of the gel fraction difference according to the following formula (1) is 10% or less:
[Formula 1]
Gel fraction difference = GF7 - GF1
(GF7 in the above formula 1 is the gel fraction according to the following formula 2 after aging at 23 占 폚 and 45% relative humidity (RH) for 7 days after the activation energy ray irradiation treatment, and GF1 is 23 占 폚 And a gel fraction according to the following formula 2 after aging at 45% RH for 1 hour)
[Formula 2]
(In the formula 2, W 1 is the weight of the test piece obtained after aging the adhesive film subjected to the activation energy ray irradiation treatment at 23 ° C and 45% RH for 1 hour or 7 days,
W 2 is the weight of the wire mesh (200 mesh)
W 3 was obtained by aging the adhesive film, putting the obtained specimen into a sample bottle, adding 30 g of ethyl acetate to the sample bottle, leaving at 25 ° C. for one day, and then drying the wire mesh and specimen at 90 ° C. for 1 hour The weight of the obtained adhesive film and the wire mesh).
90 parts by weight to 99.9 parts by weight of the (meth) acrylic ester monomer (a-1) and 0.1 part by weight of at least one of the carboxyl group-containing monomer (a-2) and the hydroxyl group- To 10 parts by weight.
Wherein the total amount of the (meth) acrylic ester monomer (a-1), the carboxyl group-containing monomer (a-2) and the hydroxyl group-containing (meth) acrylic monomer (a-3) is 100 parts by weight.
(B) 0.05 to 4 parts by weight of a photopolymerization initiator; And
(C) 0.05 to 5 parts by weight of a carbodiimide-based curing agent not containing an isocyanate group.
90 to 99.9 parts by weight of the (meth) acrylic acid ester monomer (a-1) and 0.1 to 10 parts by weight of at least one of the carboxyl group-containing monomer (a-2) and the hydroxyl group- 10 parts by weight.
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| PCT/KR2015/007726 WO2016018003A1 (en) | 2014-08-01 | 2015-07-24 | Adhesive composition, adhesive film, optical member, and adhesive sheet |
| TW104124623A TWI582190B (en) | 2014-08-01 | 2015-07-30 | Adhesive composition, adhesive film, optical member and adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6554344B2 (en) * | 2015-06-30 | 2019-07-31 | リンテック株式会社 | Adhesive sheet and display |
| TW201807050A (en) * | 2016-05-18 | 2018-03-01 | 綜研化學股份有限公司 | Photocurable resin composition, resin layer of same, and mold for imprint |
| WO2018146958A1 (en) * | 2017-02-09 | 2018-08-16 | 富士フイルム株式会社 | Half mirror, method for producing half mirror, and mirror provided with image display function |
| JP7075109B2 (en) * | 2017-04-14 | 2022-05-25 | 協立化学産業株式会社 | Photo-curing adhesive composition |
| JP7180235B2 (en) * | 2017-12-15 | 2022-11-30 | 三菱ケミカル株式会社 | Adhesive composition, and adhesive, adhesive sheet, adhesive for polarizing plate, and polarizing plate with adhesive layer using the same |
| TWI786219B (en) * | 2017-12-19 | 2022-12-11 | 日商三菱化學股份有限公司 | Solvent-free acrylic resin composition, solvent-free acrylic adhesive using the same, adhesive sheet, and method for producing solvent-free acrylic resin composition |
| JP7264598B2 (en) * | 2018-04-02 | 2023-04-25 | デクセリアルズ株式会社 | Adhesive composition and connecting structure |
| JP7196465B2 (en) * | 2018-08-24 | 2022-12-27 | 三菱ケミカル株式会社 | Adhesive composition, and adhesive and adhesive sheet using the same |
| KR20210144814A (en) * | 2019-03-28 | 2021-11-30 | 스미또모 가가꾸 가부시키가이샤 | adhesive composition |
| KR20220024417A (en) * | 2019-06-12 | 2022-03-03 | 스미또모 가가꾸 가부시키가이샤 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet and optical laminate |
| JP7420930B2 (en) * | 2019-10-16 | 2024-01-23 | コザ・ノベル・マテリアルズ・コリア・カンパニー・リミテッド | curable composition |
| US20220162359A1 (en) * | 2019-10-16 | 2022-05-26 | Lg Chem, Ltd. | Curable Composition |
| CN113853538A (en) * | 2019-10-31 | 2021-12-28 | 株式会社Lg化学 | Polarizing plate laminate and method for producing same |
| CN116034147B (en) * | 2020-08-18 | 2024-04-05 | 株式会社Lg化学 | Adhesive composition containing antistatic agent and surface protective film |
| CN112322195B (en) * | 2020-11-03 | 2023-05-16 | 西安思摩威新材料有限公司 | Ultraviolet light curing composition glue and use method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006235568A (en) | 2005-01-27 | 2006-09-07 | Lintec Corp | Adhesive for polarizing plate, and polarizing plate with adhesive and its production method |
| KR20120045998A (en) * | 2010-10-29 | 2012-05-09 | 제일모직주식회사 | Adhesive composition |
| JP5095150B2 (en) * | 2006-08-03 | 2012-12-12 | 日東電工株式会社 | Aqueous pressure sensitive adhesive composition and use thereof |
| JP2013203899A (en) | 2012-03-28 | 2013-10-07 | Lintec Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
| KR20140004294A (en) * | 2012-06-29 | 2014-01-13 | 동우 화인켐 주식회사 | Adhesive composition |
| JP5417652B1 (en) * | 2013-04-08 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Resin composition, active energy ray-polymerizable adhesive, and laminate |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4067173B2 (en) * | 1998-04-14 | 2008-03-26 | サイデン化学株式会社 | Adhesive composition |
| JP5863157B2 (en) * | 2006-12-18 | 2016-02-16 | 日東電工株式会社 | Adhesive sheet |
| JP5455362B2 (en) * | 2008-12-25 | 2014-03-26 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition and optical member using the same |
| JP5662676B2 (en) * | 2009-12-10 | 2015-02-04 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition and optical member using the same |
| JP5546973B2 (en) * | 2010-07-02 | 2014-07-09 | チェイル インダストリーズ インコーポレイテッド | Adhesive composition and optical member using the adhesive |
| CN102464960B (en) * | 2010-10-29 | 2014-10-15 | 第一毛织株式会社 | Adhesive composition, optical member, surface protective film, and adhesive sheet |
| JP2013032483A (en) * | 2011-06-28 | 2013-02-14 | Nitto Denko Corp | Optical double-sided adhesive sheet, optical member, touch panel, image display and delamination method |
| JP2015134841A (en) * | 2012-03-27 | 2015-07-27 | 日本ペイントホールディングス株式会社 | Curable resin composition for forming adhesive layer and method for integrating substrate and substrate to be adhered |
| JP2013204035A (en) * | 2012-03-29 | 2013-10-07 | Sekisui Chem Co Ltd | Adhesive tape |
| WO2014010627A1 (en) * | 2012-07-11 | 2014-01-16 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-polymerizable resin composition and laminate obtained using said resin composition |
-
2015
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006235568A (en) | 2005-01-27 | 2006-09-07 | Lintec Corp | Adhesive for polarizing plate, and polarizing plate with adhesive and its production method |
| JP5095150B2 (en) * | 2006-08-03 | 2012-12-12 | 日東電工株式会社 | Aqueous pressure sensitive adhesive composition and use thereof |
| KR20120045998A (en) * | 2010-10-29 | 2012-05-09 | 제일모직주식회사 | Adhesive composition |
| JP2013203899A (en) | 2012-03-28 | 2013-10-07 | Lintec Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
| KR20140004294A (en) * | 2012-06-29 | 2014-01-13 | 동우 화인켐 주식회사 | Adhesive composition |
| JP5417652B1 (en) * | 2013-04-08 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Resin composition, active energy ray-polymerizable adhesive, and laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201610051A (en) | 2016-03-16 |
| CN106550604A (en) | 2017-03-29 |
| JP6688019B2 (en) | 2020-04-28 |
| JP2016035046A (en) | 2016-03-17 |
| TWI582190B (en) | 2017-05-11 |
| KR101882560B1 (en) | 2018-07-26 |
| CN106550604B (en) | 2020-06-16 |
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