CN109207103A - For the bonding film and adhesive composition of polarizer, the polarizer comprising bonding film and include the optical display of polarizer - Google Patents
For the bonding film and adhesive composition of polarizer, the polarizer comprising bonding film and include the optical display of polarizer Download PDFInfo
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- CN109207103A CN109207103A CN201810728650.6A CN201810728650A CN109207103A CN 109207103 A CN109207103 A CN 109207103A CN 201810728650 A CN201810728650 A CN 201810728650A CN 109207103 A CN109207103 A CN 109207103A
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- China
- Prior art keywords
- polarizer
- methyl
- bonding film
- curing agent
- acrylate
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Classifications
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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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Abstract
This application discloses a kind of bonding film for polarizer and adhesive composition, the polarizer comprising bonding film and include the optical display of polarizer.The polarizer bonding film includes: comprising having C4‑C8(methyl) acrylate of alkyl, (methyl) acrylate with hydroxyl and there is C1‑C3(methyl) acrylic copolymer of the monomer mixture of at least one of (methyl) acrylate of alkyl and (methyl) acrylic monomer with amide groups, and meet the following Expression 1 and formula 2: 2-tan δ 1≤0.04 of<formula 1>0.20≤tan δ 2≤0.40<formula 2>tan δ wherein tan δ 1 be the bonding film for polarizer at 23 DEG C tan δ value, and tan δ 2 is the tan δ value of the bonding film for polarizer at 80 DEG C.
Description
The citation of related application
This application claims enjoy the South Korea patent application 10-2017-0084948 and 2017 that on July 4th, 2017 submits
Submit within September 14 days the equity of the South Korea patent application 10-2017-0118066 of Korean Intellectual Property Office, the entire disclosure knot
Together in herein by reference.
Technical field
The present invention relates to a kind of polarizer bonding films, a kind of adhesive composition for polarizer bonding film, packet
Polarizer containing the bonding film and the optical display comprising the polarizer.
Background technique
Liquid crystal display includes liquid crystal display panel and the polarizer that is attached on two surfaces of liquid crystal display panel.The polarizer packet
It includes polarizer and is attached to one or two surface of the polarizer to protect the protective film of the polarizer.The polarizer
It is attached on the liquid crystal display panel via polarizer with bonding film.
By the way that adhesive composition to be deposited on stripping film with predetermined thickness, then dries and polarizer bonding is made
Film.In order to be packed, be stored and/or delivered, the polarizer bonding film is with stripping film, polarizer bonding film and removing
The laminated body form of film provides.The stripping film can prevent the bonding film from being polluted by foreign substance.However, in packaging, storage
Or delivering during, the polarizer bonding film may contact with outer solid particle and understand therefore and it is depressed.It is described
This dent in bonding film, which is referred to as, to be recessed.
Although the stripping film is formed on the bonding film, it is difficult to prevent to generate in the bonding film such recessed
It falls into.Polarizer comprising this bonding film with recess will lead to undesirable screen quality.On the other hand, the polarizer is used
Bonding film is attached on the polarizer, and is cut before processing.During this process, the bonding film can be by solid
Particle collapses.It can prevent from generating recess by solid particle or even if when the bonding film is by solid particle therefore, it is necessary to one kind
Also it is capable of the bonding film of fast quick-recovery when collapsing.
It is the content or (methyl) propylene for increasing curing agent in the bonding film as the method being recessed in bonding film is reduced
The glass transition temperature of acid copolymer.However, the increase of the curing agent content will lead to the polarizer at high temperature
Warpage.In addition, the raising of the glass transition temperature of (methyl) acrylic copolymer will lead to the polarizer in height
The lower warpage of temperature.
Background technique of the invention is disclosed in Japanese Unexamined Patent Publication No.2015-010192.
Summary of the invention
It is an aspect of the invention to provide one kind can be in the processing of the bonding film, cutting, packaging and/or storage period
Between inhibit and/or fast quick-recovery described in bonding film, for example, the polarizer bonding film of the recess due to caused by solid particle.
Another aspect of the present invention is to provide one kind and is able to suppress to be drawn since polarizer (polarizer) is shunk at high temperature
The polarizer bonding film of the warpage risen.
It is another aspect of the present invention to provide it is a kind of can by mitigate the contraction of polarizer at high temperature realize it is excellent
Light leakage inhibiting effect polarizer bonding film.
It is a further aspect of the present invention to provide a kind of polarizer bonding films, in high temperature or under high temperature/high humidity conditions
Good durability is shown, and is inhibiting corrosion side when being attached to the metal adhesion body including indium tin oxide (ITO) film
Face has good nature and doing over again property.
According to an aspect of the present invention, a kind of polarizer bonding film, comprising: comprising having C4-C8(methyl) of alkyl
Acrylate, (methyl) acrylate with hydroxyl and have C1-C3(methyl) acrylate of alkyl and have amide groups
At least one of (methyl) acrylic monomer monomer mixture (methyl) acrylic copolymer, and meet following
Formula 1 and formula 2:
<formula 1>
0.20≤tanδ2≤0.40
<formula 2>
tanδ2–tanδ1≤0.04
(wherein tan δ 1 is the tan δ value of the polarizer bonding film at 23 DEG C, and tan δ 2 is described at 80 DEG C
The tan δ value of polarizer bonding film).
According to another aspect of the present invention, a kind of adhesive composition for polarizer includes: comprising having C4-C8Alkane
(methyl) acrylate of base, (methyl) acrylate with hydroxyl and there is C1-C3(methyl) acrylate of alkyl and
(methyl) acrylic copolymer of the monomer mixture of at least one of (methyl) acrylic monomer with amide groups；Its
In the following Expression 1 and formula 2 met by the polarizer bonding film that the adhesive composition for polarizer is formed:
<formula 1>
0.20≤tanδ2≤0.40
<formula 2>
tanδ2–tanδ1≤0.04
(wherein tan δ 1 is the tan δ value of the polarizer bonding film at 23 DEG C, and tan δ 2 is described at 80 DEG C
The tan δ value of polarizer bonding film).
In accordance with a further aspect of the present invention, a kind of polarizer, including polarizer bonding film according to the present invention.
According to another aspect of the invention, a kind of optical display, including polarizer bonding film according to the present invention or
Polarizer according to the present invention.
Detailed description of the invention
Fig. 1 is the schematic diagram for measuring creep.
Fig. 2 is the schematic diagram for measuring light leakage.
Specific embodiment
Now with reference to attached drawing detailed description of the present invention embodiment, to provide to those skilled in the art to of the invention
Comprehensive understanding.It should be understood that the present invention can be implemented in various ways, and it is not limited to following implementation.
Herein, term " polarizer bonding film " (or " bonding film for polarizer ") and " for the viscous of polarizer
Mixture composite " can be indicated simply by the term " bonding film " and " adhesive composition " respectively.
Herein, term " (methyl) acryloyl group " refers to acryloyl group and/or methylacryloyl.
Hereinafter, the polarizer bonding film by description according to embodiment of the present invention.
The polarizer adhesive film according to embodiment of the present invention includes: comprising having C4-C8Alkyl
(methyl) acrylate, (methyl) acrylate with hydroxyl and have C1-C3(methyl) acrylate of alkyl and have
(methyl) acrylic copolymer of the monomer mixture of at least one of (methyl) acrylic monomer of amide groups, and it is full
Sufficient the following Expression 1 and formula 2:
<formula 1>
0.20≤tanδ2≤0.40
<formula 2>
tanδ2–tanδ1≤0.04
(wherein tan δ 1 is the tan δ value of the polarizer bonding film at 23 DEG C, and tan δ 2 is described at 80 DEG C
The tan δ value of polarizer bonding film).
It is described when the polarizer bonding film meets formula 1 and formula 2 and when including (methyl) acrylic copolymer
Bonding film can inhibit during the processing of the bonding film, cutting, packaging and/or storage and/or fast quick-recovery, for example, by
Recess caused by solid particle and in the bonding film, and be able to suppress since the polarizer (polarizer) is in high temperature
Warpage caused by lower contraction.Meet the formula 1 but the bonding film for being unsatisfactory for formula 2 does not have inhibition due to the polarizer
The effect of warpage caused by shrinking at high temperature does not have the effect of the recess in bonding film described in inhibition or fast quick-recovery yet,
To cause processability decline.In one embodiment, the bonding film meets formula 1 and 2 and with about 18 μm or more
It is small, for example, about 9 μm or smaller, or about 8 μm or smaller recess.Within this range, the bonding film will not cause recess or recessed
It falls into slightly, and can be consequently used for polarizer.Herein, term " recess " refers to the depth being recessed in the bonding film or recessed
It falls into.
It is preferred that the bonding film has about 0.21~about 0.38, more preferably from about 0.23~about 0.35 2 value of tan δ.It is preferred that institute
Stating bonding film has about -0.20~about 0.02 difference of (tan δ 2-tan δ 1).1 value of tan δ of the bonding film is about 0.10~
About 0.50, preferably from about 0.15~about 0.45, more preferably from about 0.18~about 0.45.Within this range, the bonding film can satisfy
The formula 1 and 2.
In one embodiment, the bonding film can satisfy formula 3:
<formula 3>
tanδ2/tanδ1<1.1
(wherein tan δ 1 is the tan δ value of the polarizer bonding film at 23 DEG C, and tan δ 2 is described at 80 DEG C
The tan δ value of polarizer bonding film).
When bonding film meets formula 3, even if the bonding film is not included carboxylic acid group and can inhibit to be existed due to polarizer
Warpage caused by contraction under high temperature, and be able to suppress or fast quick-recovery described in recess in bonding film.It is preferred that described viscous
Closing film has the ratio between about 0.50~about 1.05 tan δ 2 and tan δ 1 (tan δ 2/tan δ 1).
The bonding film can be formed by the adhesive composition for polarizer, and described adhesive composition includes: containing
Have with C4-C8(methyl) acrylate of alkyl, (methyl) acrylate with hydroxyl and there is C1-C3(the first of alkyl
Base) at least one of acrylate and (methyl) acrylic monomer with amide groups monomer mixture (methyl) propylene
Acid copolymer；And curing agent.
It is described that there is C4-C8(methyl) acrylate of alkyl forms the matrix of the bonding film and improves the bonding film
Mechanical strength, while other components being allowed to be contained in the monomer mixture with amount appropriate, to make the bonding film
Meet formula 1 and 2.For example, described have C4-C8(methyl) acrylate of alkyl be free from hydroxyl without carboxylic monomer, and can be with
Including (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid penta
Ester, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate
(methyl) Isooctyl acrylate monomer, but it is not limited only to this.These can be used alone or use as its mixture.
In one embodiment, described that there is C4-C8(methyl) acrylate of alkyl may include in homopolymer phase
(methyl) acrylate for being -45 DEG C or lower, preferably -70~-45 DEG C with glass transition temperature.In the range, institute
It states with C4-C8(methyl) acrylate of alkyl allows the bonding film together with the other components in the monomer mixture
Meet formula 1 and 2.For example, described have C4-C8(methyl) acrylate of alkyl may include n-butyl acrylate, acrylic acid 2-
At least one of ethylhexyl and the just own ester of acrylic acid, but not limited to this.
It is described that there is C4-C8(methyl) acrylate of alkyl can with about 40mol%~about 78mol%, for example,
40mol%, 41mol%, 42mol%, 43mol%, 44mol%, 45mol%, 46mol%, 47mol%, 48mol%,
49mol%, 50mol%, 51mol%, 52mol%, 53mol%, 54mol%, 55mol%, 56mol%, 57mol%,
58mol%, 59mol%, 60mol%, 61mol%, 62mol%, 63mol%, 64mol%, 65mol%, 66mol%,
67mol%, 68mol%, 69mol%, 70mol%, 71mol%, 72mol%, 73mol%, 74mol%, 75mol%,
76mol%, 77mol% or 78mol%, preferably from about 43mol%~about 78mol% amount are present in the monomer mixture.
Within this range, the bonding film is able to maintain mechanical strength, while meeting formula 1 and formula 2.
Described (methyl) acrylate with hydroxyl can improve the bonding film and reacting with the curing agent
Adhesive strength.Described (methyl) acrylate with hydroxyl may include containing the C at least one hydroxyl1-C20Alkane
(methyl) acrylate of base.For example, described (methyl) acrylate with hydroxyl may include selected from (methyl) acrylic acid
2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxy butyl ester, (methyl) acrylic acid 4- hydroxy butyl ester, (first
Base) the own ester of acrylic acid 6- hydroxyl, at least one of the group of the chloro- 2- hydroxypropyl acrylate of (methyl) acrylic acid 1- and combinations thereof composition.
Described (methyl) acrylate with hydroxyl can with about 0.1mol%~about 20mol%, such as 0.1mol%,
0.5mol%, 1mol%, 2mol%, 3mol%, 4mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%,
10mol%, 11mol%, 12mol%, 13mol%, 14mol%, 15mol%, 16mol%, 17mol%, 18mol%,
19mol% or 20mol%, about 0.1mol%~about 15mol%, preferably from about 1mol%~about 10mol%, more preferably from about 1mol%
The amount of~about 5mol% is present in the monomer mixture.Within this range, the bonding film is able to maintain mechanical strength, together
When meet formula 1 and formula 2.
It is described with C that the monomer mixture may include about 10mol%~about 40mol%1-C3(methyl) of alkyl
Acrylate and described at least one of (methyl) acrylic monomer with amide groups.Therefore, the bonding film can
Meet formula 1 and 2.
In some embodiments, the monomer mixture may include described with C1-C3(methyl) acrylic acid of alkyl
Ester, and can be without described (methyl) acrylic monomer with amide groups.In other embodiments, the monomer is mixed
Closing object may include described (methyl) acrylic monomer with amide groups, and can have C without described1-C3Alkyl
(methyl) acrylate.In other embodiments, the monomer mixture can include described with C simultaneously1-C3Alkyl
(methyl) acrylate and described (methyl) acrylic monomer with amide groups.
It is preferred that the monomer mixture has C with described1-C3(methyl) acrylate of alkyl and it is described have amide
At least one of (methyl) acrylic monomer of base has about 5~about 150 DEG C of glass transition in homopolymer phase
Temperature.Within this range, the monomer mixture allows the bonding film to meet formula 1 and formula 2, while improving its durability.
It is described that there is C1-C3(methyl) acrylate of alkyl may include (methyl) methyl acrylate, (methyl) acrylic acid
At least one of ethyl ester and (methyl) propyl acrylate, but not limited to this.It is preferred that described have C1-C3(methyl) third of alkyl
Olefin(e) acid ester has 5~50 DEG C of glass transition temperature in homopolymer phase.Within this range, the bonding film can satisfy formula
1 and formula 2, while improving its durability.
It is described that there is C1-C3(methyl) acrylate of alkyl can with 0mol%~about 40mol%, for example, 0mol%,
1mol%, 2mol%, 3mol%, 4mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%, 10mol%,
11mol%, 12mol%, 13mol%, 14mol%, 15mol%, 16mol%, 17mol%, 18mol%, 19mol%,
20mol%, 21mol%, 22mol%, 23mol%, 24mol%, 25mol%, 26mol%, 27mol%, 28mol%,
29mol%, 30mol%, 31mol%, 32mol%, 33mol%, 34mol%, 35mol%, 36mol%, 37mol%,
38mol%, 39mol% or 40mol%, about 1mol%~about 40mol%, or about 5mol%~about 40mol% amount are present in
In the monomer mixture.Within this range, the monomer mixture allows the bonding film to meet the formula 1 and 2, changes simultaneously
Into its durability.
Described (methyl) acrylic monomer with amide groups may include (methyl) acrylic compounds containing morpholinyl
Monomer, such as at least one of (methyl) acryloyl morpholine and (methyl) acrylamide, but not limited to this.Preferably, described
(methyl) acrylic monomer with amide groups has about 100~about 200 DEG C of glass transition temperature in homopolymer phase.
It is preferred that (methyl) acrylic monomer with amide groups includes (methyl) acrylic monomer containing morpholinyl, such as
(methyl) acryloyl morpholine.Within this range, the monomer mixture allows the bonding film to meet the formula 1 and formula 2, simultaneously
Improve its durability.
Described (methyl) acrylic monomer with amide groups can with 0mol%~about 40mol%, for example,
0mol%, 1mol%, 2mol%, 3mol%, 4mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%,
10mol%, 11mol%, 12mol%, 13mol%, 14mol%, 15mol%, 16mol%, 17mol%, 18mol%,
19mol%, 20mol%, 21mol%, 22mol%, 23mol%, 24mol%, 25mol%, 26mol%, 27mol%,
28mol%, 29mol%, 30mol%, 31mol%, 32mol%, 33mol%, 34mol%, 35mol%, 36mol%,
37mol%, 38mol%, 39mol% or 40mol%, about 1mol%~about 40mol%, about 1mol%~about 20mol%, example
Such as, about 1mol%~about 15mol%, for example, about 5mol%~about 15mol% amount is present in the monomer mixture.?
Within the scope of this, the monomer mixture allows the bonding film to meet formula 1 and formula 2, while improving its durability.
The monomer mixture can further include (methyl) acrylic monomer with tertiary amine group.It is described to have
(methyl) acrylic monomer of tertiary amine group can improve the rate of polymerization of described (methyl) acrylic copolymer and described
The rate of ageing of bonding film.
Described (methyl) acrylic monomer with tertiary amine group may include having the C containing tertiary amine group1-C5Alkyl
(methyl) acrylate.For example, described (methyl) acrylic monomer with tertiary amine group may include (methyl) propylene
Acid dialkyl aminoalkyl ester, and may include (methyl) acrylate, (methyl) acrylic acid dimethylamino
Base propyl ester, (methyl) acrylate butyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid diethyl
In base amino propyl ester, (methyl) acrylic acid diethylamino butyl ester and (methyl) acrylic acid dibutylamino ethyl ester at least it
One.
Described (methyl) acrylic monomer with tertiary amine group can with 0mol%~about 15mol%, for example,
0mol%, 0.01mol%, 0.02mol%, 0.03mol%, 0.04mol%, 0.05mol%, 0.06mol%, 0.07mol%,
0.08mol%, 0.09mol%, 0.1mol%, 0.2mol%, 1mol%, 2mol%, 3mol%, 4mol%, 5mol%,
6mol%, 7mol%, 8mol%, 9mol%, 10mol%, 11mol%, 12mol%, 13mol%, 14mol%, 15mol%,
About 0.001mol%~about 15mol%, particularly about 0.01mol%~about 10mol%, more specifically about 0.01mol%~about
The amount of 1mol% is present in the monomer mixture.Within this range, the monomer mixture can improve institute at room temperature
The ageing rate for the adhesive composition of polarizer or its dry products is stated, while improving its curing reaction.
The monomer mixture can further include (methyl) acrylate with alicyclic group and have aromatics
At least one of (methyl) acrylate of group.(methyl) acrylate with alicyclic group and described have
(methyl) acrylate of aromatic group can improve the light leakage characteristic of the bonding film.
(methyl) acrylate and described (methyl) acrylate with aromatic group with alicyclic group
At least one of can with 0mol%~about 20mol%, for example, 0mol%, 1mol%, 2mol%, 3mol%, 4mol%,
5mol%, 6mol%, 7mol%, 8mol%, 9mol%, 10mol%, 11mol%, 12mol%, 13mol%, 14mol%,
15mol%, 16mol%, 17mol%, 18mol%, 19mol% or 20mol%, about 0.001mol%~about 20mol%, example
Such as, about 5mol%~about 20mol%, for example, about 10mol%~about 15mol% amount is present in the monomer mixture.?
Within the scope of this, the monomer mixture can improve the light leakage characteristic of the bonding film.
Described (methyl) acrylate with alicyclic ring group group is with C5-C20Monocycle or polycyclic alicyclic group
(methyl) acrylate, and may include (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid
At least one of two ring pentyl esters, (methyl) acrylic methyl cyclohexyl and (methyl) acrylic acid dicyclopentenyl ester.These can be with
It is used alone or as its mixture.It is preferred that (methyl) acrylate with alicyclic group includes (methyl) third
At least one of olefin(e) acid cyclohexyl and (methyl) isobornyl acrylate.
Described (methyl) acrylate with aromatic group may include with C6-C20Aryl or C7-C20Aralkyl
(methyl) acrylate.Specifically, described (methyl) acrylate with aromatic group may include (methyl) acrylic acid
Benzyl ester, but not limited to this.
The monomer mixture is free of (methyl) acrylic monomer with carboxylic acid group.The bonding film includes no carboxylic
(methyl) acrylate copolymer of acidic group could inhibit the corrosion to metal adhesion body.(methyl) acrylic copolymer can
With about 5mg KOH/g or smaller, particularly from about 1mg KOH/g or smaller acid value.In the range, described (methyl) propylene
Acid copolymer can directly or indirectly realize the corrosion inhibition about adherend.
The monomer mixture can be without (methyl) acrylate with chain alkyl.When the monomer mixture packet
When containing (methyl) acrylate with chain alkyl, (methyl) acrylic copolymer cannot obtain of the invention advantageous
Effect.Described " (methyl) acrylate with chain alkyl " can refer to C10-C25(methyl) acrylic acid of alkyl
Ester.
(methyl) acrylic copolymer is with about -30 DEG C~about -10 DEG C, preferably from about -25 DEG C~about -10 DEG C, more
Preferably from about -22 DEG C~about -13 DEG C of glass transition temperature.Within this range, the bonding film is able to suppress recess and warpage.
(methyl) acrylic copolymer can have about 500,000g/mol~about 1,500,000g/mol, preferably
About 500,000g/mol~about 1,000,000g/mol, more preferably from about 700,000g/mol~about 1,000,000g/mol weight is equal
Molecular weight.Within this range, the bonding film is able to suppress recess and warpage.
(methyl) acrylic copolymer can be prepared by typical polymerization.The polymerization can wrap
Include typical method well known by persons skilled in the art.For example, (methyl) acrylic copolymer can be to the monomer
After adding initiator in mixture, by typical copolymer polymerization method, for example, suspension polymerization, emulsion polymerization, polymerisation in solution
Deng preparation.Polymerization can about 65 DEG C~about 70 DEG C at a temperature of carry out about 6 hours~about 8 hours.The initiator can be
Typical initiator, including azo type polymerization initiator and/or peroxidic polymerization initiators, such as benzoyl peroxide or peroxide
Acetyl.
The curing agent can provide adhesive strength and reacting with (methyl) acrylic copolymer.It is described solid
Agent may include thermal curing agents and light curing agent.The curing agent can be relative to (methyl) third described in 100 parts by weight
About 0.001 parts by weight of olefin(e) acid analog copolymer~about 5 parts by weight, for example, 0.001,0.1,0.5,1.0,1.5,2.0,2.5,3.0,
3.5,4.0,4.5,5.0 parts by weight, preferably from about 0.001 parts by weight~about 3 parts by weight, more preferably from about 0.05 parts by weight~about 3 weights
Part, about 0.3 parts by weight~about 3 parts by weight, or about 0.1 parts by weight~about 2.5 parts by weight amount is measured to exist.Within this range, institute
Adhesive effect can be provided to described adhesive composition by the crosslinking of described adhesive composition by stating curing agent, be prevented simultaneously
Only due to excessively being deteriorated using caused transparency.
The thermal curing agents may include at least one of isocyanate curing agent, for example, polyalkylene glycol does not change
Property at least one of isocyanate curing agent and polyalkylene glycol modified isocyanate curing agent；Metallo-chelate solidification
Agent；Epoxy hardener；Aziridine hardener；Amine hardener；And thermal polymerization.The thermal curing agents preferably include isocyanic acid
At least one of ester curing agent and metallo-chelate curing agent.These can be used alone or are used with a combination thereof.
The isocyanate curing agent can be difunctionality or polyfunctional isocyanate's curing agent, preferably difunctionality to six officials
The isocyanate curing agent of energy, but not limited to this.
In one embodiment, the isocyanate curing agent may include the unmodified isocyanide of the polyalkylene glycol
At least one of acid esters curing agent and polyalkylene glycol modified isocyanate curing agent.
The unmodified isocyanate curing agent of polyalkylene glycol may include not comprising polyalkylene glycol mono member
Isocyanate curing agent.For example, the unmodified isocyanate curing agent of polyalkylene glycol may include comprising meta-xylene
The xylene diisocyanate (XDI) of diisocyanate etc., the di-2-ethylhexylphosphine oxide comprising 4,4' methylene bis (phenyl isocyanate) etc.
(phenyl isocyanate) (MDI), naphthalene diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate and isophorone
At least one of diisocyanate.
The polyalkylene glycol modified isocyanate curing agent may include wherein difunctionality or polyfunctional poly- alkylene
The solidification that one or more isocyanate groups in the unmodified isocyanate curing agent of base glycol are modified by polyalkylene glycol
Agent.The polyalkylene glycol modified isocyanate curing agent can reduce recess if not being excessively used, and can pass through
Reduce that the creep under high temperature generates and inhibits polarizer light leakage at high temperature and warpage.Particularly, even if working as the bonding film
When being pressed by solid particle, original state can also be quickly recovered to by the bonding film that described adhesive composition is formed,
Thus improve machinability.
The polyalkylene glycol modified isocyanate curing agent can by by polyalkylene glycol and difunctionality or it is more
Functional isocyanate curing agent is mixed according to predetermined molar ratio, is then reacted and is prepared at a predetermined temperature.The isocyanates
One or more isocyanate groups in curing agent are modified and reacting with polyalkylene glycol.The polyalkylene two
Alcohol modified isocyanate curing agent can by by the polyalkylene glycol and difunctionality or polyfunctional isocyanate's curing agent
With the mixing of about 1:2~about 1:6 molar ratio, then reacts and prepare at about 40~about 70 DEG C.Herein, it is reacted to improve
The catalysts of such as DBTDL (dibutyltin dilaurate) can be used in yield.
It is preferred that the polyalkylene glycol modified isocyanate curing agent is bifunctional isocyanate's curing agent.Using described
Curing agent, even if (methyl) acrylic copolymer also can in the case where the bonding film has dent (recess)
It is sufficiently solidified and allows the fast quick-recovery of the bonding film.
The polyalkylene glycol can have about 300g/mol~about 5000g/mol, and preferably from about 400g/mol~about
The number-average molecular weight (Mn) of 3000g/mol.In the range, the polyalkylene glycol can inhibit polarizer at high temperature
Warpage allows (methyl) acrylic copolymer to occur and preventing the number-average molecular weight of the curing agent to be excessively increased
Effectively solidification, and improve recess inhibiting effect.
The polyalkylene glycol includes multiple aklylene glycol repetitive units with primary alconol carbon or secondary alcohol carbon, for example,
Polypropylene glycol (PPG), polyethylene glycol (PEG) etc..By the modified isocyanic acid of the polyol (for example, trimethylolpropane) with tertiary alcohol carbon
Ester curing agent rigidly increases at high temperature, and warpage or recess inhibiting effect is thus made to be deteriorated.
The isocyanate curing agent of two function or higher functional refers to two functions to six functional isocyanate curing agent,
It and may include the xylene diisocyanate (XDI) comprising m xylene diisocyanate etc., comprising 4,4' methylene bis
Di-2-ethylhexylphosphine oxide (phenyl isocyanate) (MDI), the naphthalene diisocyanate, toluene di-isocyanate(TDI), six of (phenyl isocyanate) etc.
At least one of methylene diisocyanate and isophorone diisocyanate.It is preferred that the isocyanates with aromatic group is solid
Agent, it may for example comprise the xylene diisocyanate (XDI) of m xylene diisocyanate including 4,4'- di-2-ethylhexylphosphine oxide (benzene
Based isocyanate) di-2-ethylhexylphosphine oxide (phenyl isocyanate) (MDI) etc. can use.It is described bifunctional or higher functional different
Cyanate curing agent can reduce the refractive index difference together with described (methyl) acrylic monomer with aromatic group, by
This further increases the transparency of the bonding film.
The polyalkylene glycol modified isocyanate curing agent can have about 350g/mol~about 5000g/mol, excellent
Select about 450g/mol~about 4000g/mol weight average molecular weight.In the range, the polyalkylene glycol modified isocyanate
Curing agent can ensure the cured effect of (methyl) acrylic copolymer and inhibit the effect of the warpage under high temperature.
In one embodiment, the bonding film comprising the polyalkylene glycol modified isocyanate curing agent is at 85 DEG C
Under can have about 200 μm or bigger, for example, about 250 μm or bigger, for example, about 250 μm~about 800 μm of creep.In this model
In enclosing, the bonding film is able to suppress the light leakage and warpage of polarizer.
The metallo-chelate curing agent may include the complex of the polyvalent metal coordination bonding of such as aluminium.Example
Such as, the metallo-chelate curing agent may include aluminium base chelate compound, such as three (ethyl acetoacetate) aluminium, acetoacetate
Ethyl ester aluminum-diisopropoxide and aluminium tris(acetylacetonate).
The thermal polymerization may include in azo compound, peroxide compound and redox compound
At least one of.The example of the peroxide compound may include: inorganic peroxide such as potassium hyperchlorate, ammonium persulfate and
Hydrogen peroxide；And organic peroxide, such as peroxide diacyl, peroxydicarbonate, peroxy esters, tetramethyl butyl peroxide neodecanoic acid
Ester, two (4- butylcyclohexyl) peroxydicarbonates, two (2- ethylhexyl) peroxy carbonates, butyl peroxy neodecanoic acid ester, two
Peroxydicarbonate, diisopropyl peroxydicarbonate, diethoxy ethyl peroxydicarbonate, diethoxy hexyl mistake
Two carbonic ester of oxygen, hexyl peroxydicarbonate, dimethoxybutyl peroxydicarbonate, bis- (3- methoxyl group -3- methoxyl group fourths
Base) peroxydicarbonate, dibutyl peroxydicarbonate, two cetyl peroxydicarbonates, two carbonic acid of myristyl peroxide
Ester, 1,1,3,3- tetramethyl butyl peroxypivalic acid ester, hexyl peroxypivalic acid ester, butyl peroxy pivalate, peroxide front three
Base hexanoyl, dimethyl hydroxyl butyl peroxy neodecanoic acid ester, amyl peroxy neodecanoic acid ester, butyl peroxy neodecanoic acid ester, t-butyl peroxy
New heptanoate, amyl peroxy pivalate, tbutylperoxypivalate, t-amyl peroxy -2 ethyl hexanoic acid ester, peroxide laurel
Acyl, two lauroyl of peroxide, two caprinoyl of peroxide, benzoyl peroxide and Benzoyl Peroxide.
It is preferred that the thermal curing agents are relative to about 0.001 weight of (methyl) acrylic copolymer described in 100 parts by weight
Part~about 5 parts by weight are measured, for example, 0.001,0.1,0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0 parts by weight,
Preferably from about 0.001 parts by weight~about 3 parts by weight, more preferably from about 0.05 parts by weight~about 3 parts by weight, about 0.3 parts by weight~about 3 weights
Part is measured, or about 0.1 parts by weight~about 2.5 parts by weight amount exists.Within this range, the thermal curing agents can be by described viscous
The crosslinking of mixture composite and provide adhesive effect to described adhesive composition, while preventing due to excessively using caused
Lightness deterioration.
The light curing agent may include that at least one of (methyl) acrylate of two functions to six functions and light draw
Send out agent.
(methyl) acrylate of two function to six functions include in bifunctional acrylate one of, such as Isosorbide-5-Nitrae-fourth
Glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, poly- second
Glycol (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) acrylate, bicyclopentyl two (methyl) acrylate,
Caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified two (methyl) acrylate, two (methyl)
Acryloyl-oxyethyl isocyanuric acid ester, allylation cyclohexyl two (methyl) acrylate, Tricyclodecane Dimethanol (methyl)
Acrylate, dihydroxymethyl bicyclopentane two (methyl) acrylate, ethylene-oxide-modified two (first of hexahydrophthalic acid
Base) modified trimethyl propane two (methyl) propylene of acrylate, Tricyclodecane Dimethanol (methyl) acrylate, neopentyl glycol
Acid esters, (methyl) acrylate of adamantane two and bis- [4- (2- acryloyloxyethoxy) phenyl] fluorenes of 9,9-；Trifunctional propylene
Acid esters, such as trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid modified two seasons penta
Tetrol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, the trimethylolpropane tris (first of epoxy pronane modification
Base) acrylate, trifunctional urethanes (methyl) acrylate and three (methyl) acryloyl-oxyethyl isocyanuric acids
Ester；The acrylate of tetrafunctional, such as (methyl) acrylate of diglycerol four and pentaerythrite four (methyl) acrylate；Five functions
Acrylate, such as dipentaerythritol five (methyl) acrylate；With six functional acrylates, such as dipentaerythritol six (methyl) third
Olefin(e) acid ester, caprolactone modification dipentaerythritol six (methyl) acrylate and urethanes (methyl) acrylate (for example,
The reaction product of isocyanate-monomer and trimethylolpropane tris (methyl) acrylate).
Two to six function (methyl) acrylate can be with total relative to (methyl) acrylic compounds described in 100 parts by weight
About 0.1 parts by weight of polymers~about 5.0 parts by weight, for example, 0.1,0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0
Parts by weight, preferably from about 0.1 parts by weight~about 1.0 parts by weight amount exist.Within this range, pass through described adhesive composition
Crosslinking, the light curing agent can provide adhesive effect for described adhesive composition, while prevent due to excessively using causing
Transparency deterioration.
The photoinitiator can be any initiator, draw as long as the initiator can be generated free radicals by illumination
Play the photopolymerization of described adhesive composition.For example, the photoinitiator may include benzoin, hydroxy-ketone, amino ketones, phosphine oxide
Initiator etc..
The photoinitiator can with about 0.1 parts by weight of (methyl) acrylic copolymer relative to 100 parts by weight~
About 5.0 parts by weight, for example, 0.1,0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0 parts by weight, preferably from about 0.1
Parts by weight~about 2.0 parts by weight amount exists.Within this range, the photoinitiator can pass through described adhesive composition
It is crosslinked and provides adhesive effect for described adhesive composition, while preventing due to excessively being deteriorated using caused transparency.
Described adhesive composition may include solvent.What the solvent can improve described adhesive composition can coating
Property, while preventing the self-curing of described adhesive composition.The solvent can be known to the skilled in the art typical molten
Agent.For example, the solvent may include at least one of methyl ethyl ketone, ethyl acetate and toluene.
Described adhesive composition can further include silane coupling agent, reprocess agent (reworking agent), be solid
Change at least one of catalyst, antistatic agent and curing accelerator.
The silane coupling agent can be realized the bonding film that high adhesion force is shown to the adherend of such as glass.The silicon
Alkane coupling agent may include any typical silane coupling agent well known by persons skilled in the art.For example, the silane coupling agent
It may include selected from by the silicon compound with epoxy construction, such as 3- glycidoxypropyltrimewasxysilane, 3- shrink
Glycerol oxygroup hydroxypropyl methyl dimethoxysilane and 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane；Containing polymerizable insatiable hunger
With the silicon compound of group, such as vinyltrimethoxysilane, vinyltriethoxysilane and (methyl) acryloxy third
Base trimethoxy silane；Amino-containing silicon compound, such as 3- TSL 8330, N- (2- amino-ethyl) -3- ammonia
Base propyl trimethoxy silicane and N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane；With 3- chloropropyl front three
At least one of the group of oxysilane composition, but not limited to this.
Relative to (methyl) acrylic copolymer described in 100 parts by weight, the silane coupling agent can be with about 0.001
Parts by weight~about 5 parts by weight, particularly from about 0.001 parts by weight~about 3 parts by weight amount exist.Within this range, the bonding
Film can show good durability and with the small change of time experience component and physical property.
What the reprocessing agent can improve the bonding film can re-workability and may include polysiloxane oligomers
Or the mixture comprising it.Relative to (methyl) acrylic copolymer described in 100 parts by weight, the reprocessing agent can be with
About 0.001 parts by weight~about 5 parts by weight, particularly from about 0.005 parts by weight~about 1 parts by weight amount exist.Within this range,
The reprocessing agent can improve can performance of the re-workability without influencing the polarizer bonding film.
The antistatic agent generates electrostatic during bonding film reprocessing for inhibiting, and may include typical
Antistatic agent.Relative to (methyl) acrylic copolymer described in 100 parts by weight, the antistatic agent can be with about 0.001
Parts by weight~about 5 parts by weight, particularly from about 0.1 parts by weight~about 3 parts by weight amount exist.Within this range, described antistatic
Agent can provide performance of the anti-static function without influencing the polarizer bonding film.
The curing catalysts may include being selected from by boron compound, for example, the complex compound of boron trifluoride, especially trifluoro
Change the ether complexes of boron, the tetrahydrofuran complex (BF of boron trifluoride3- THF), the aniline complex compound (BF of boron trifluoride3Benzene
Amine), especially BF3·O(CH3)2(boron trifluoride dimethyl conjunction object), BF3·O(C2H5)2(boron trifluoride Anaesthetie Ether closes
Object) etc.；Phosphine compound, for example, triphenylphosphine, tributylphosphine, three (p-methylphenyl) phosphines, three (nonyl phenyl) phosphines, triphenyl
Phosphine/triphenyl borine acid esters, tetraphenylborate etc.；Secondary amine or tertiary amine compound, for example, triethylamine, α-tertiary amine compound (example
Such as, KH-30, Kukdo), such as benzyl diethylamine or benzyl dimethylamine；Imidazolium compounds, for example, 2-methylimidazole, 2- phenyl
Imidazoles, 2- phenyl -4-methylimidazole etc.；Sulfoacid compound, for example, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acids, naphthalene
At least one of groups of compositions such as disulfonic acid, methanesulfonic acid, methane-disulfonic acid, phenolsulfonic acid.Relative to described in 100 parts by weight
(methyl) acrylic copolymer, the curing catalysts can with about 0.01 parts by weight~about 5 parts by weight, particularly from about 0.05
Parts by weight~about 2 parts by weight amount exists.Within this range, the curing catalysts can reduce solidification rate.
Described adhesive composition can further include typical additive.The additive may include UV absorption
Agent, antioxidant, the resin, the plasticizer that assign adhesiveness etc..Relative to (methyl) acrylic copolymer described in 100 parts by weight
Object, the additive can be with about 0.001 parts by weight~about 5 parts by weight, particularly about 0.01 parts by weight~about 1 parts by weight amount
In the presence of.Within this range, its intrinsic effect may be implemented in the additive, the property without will affect the polarizer bonding film
Energy.
Described adhesive composition can have about 1,000cP~about 4,000cP viscosity at about 25 DEG C.In this range
Interior, described adhesive composition can promote the thickness of the bonding film to adjust, and form bonding film without generating spot, and
It is capable of providing uniform coating surface.
The bonding film be it is optically transparent, be applied to optical display.Particularly, in the wavelength of 380nm~780nm
Under, the bonding film can have about 85% or more, more specifically about 85%~about 95% light transmittance.
The bonding film can have about 100 μm or smaller, particularly from about 5 μm~about 50 μm of thickness.Within this range,
The bonding film is suitable for optical display.
Sample on the glass substrate comprising the bonding film can have the warpage less than about 15mm at 85 DEG C.
Within this range, the bonding film is able to suppress the warpage of polarizer at high temperature, so that it is guaranteed that good screen at high temperature
Visibility.
Described adhesive film can by by described adhesive composition coating to predetermined thickness, then about 25 DEG C~about
It is made after dry and aging under 35 DEG C and about 30%~about 60%RH (relative humidity) of steady temperature/damp condition.
Then, the polarizer and optical display of embodiment according to the present invention will be described.
Polarizer according to embodiment of the present invention may include the institute of embodiment according to the present invention
State polarizer bonding film.The polarizer can be by will be attached to polarizer according to the bonding film of the embodiment
A surface on or by by according to the described adhesive composition of the embodiment be coated on polarizer a surface
It is upper to reach predetermined thickness, then aging and be made.
Optical display according to embodiment of the present invention may include bonding film according to the present invention or
Polarizer according to the present invention.The optical display may include liquid crystal display and organic light-emitting diode display
Device, but not limited to this.Optical display according to the present invention may include flexible display.
The polarizer may include polarizer, the optical film formed at least one surface of the polarizer and
The bonding film formed at least one surface of the optical film.The polarizer and optical film with it is known to those skilled in the art
Those of it is identical.The polarizer can have about 25 μm~about 100 μm of thickness, particularly about 50 μm~about 85 μm of thickness
Degree.In this thickness range, the polarizer can be used in optical display.The polarizer may include polarizer, in institute
State the optical film formed at least one surface of polarizer, and the bonding formed at least one surface of the optical film
Film.The optical film is optical clear film, and may include the cellulose membrane comprising tri acetyl cellulose membrane, comprising gathering to benzene two
Polyester film, polycarbonate membrane, acrylic film, the cyclo-olefin-polymer films etc. of formic acid second diester film.
Liquid crystal display may include the liquid crystal display comprising IPS liquid crystal, but not limited to this.
It then, will the present invention will be described in more detail referring to some embodiments.It is to be noted, however, that these embodiments
It is only used for the purpose of illustration, without being construed to the limitation present invention in any way.
Prepare embodiment 1:(methyl) acrylic copolymer preparation
In the 1L reactor equipped with the cooler for promoting temperature to adjust, while purging using nitrogen, it is placed in acetic acid second
Ester.Then, by 100 parts by weight include the n-butyl acrylate (BA) of 66.975mol%, 20mol% methyl acrylate (MA),
The acryloyl morpholine (ACMO) of 10mol%, the acrylic acid 4- hydroxy butyl ester (4-HBA) of 3mol% and 0.025mol% acrylic acid diformazan
The monomer mixture of base amino ethyl ester (DMAEA) is added in the reactor.In addition, by ethyl acetate and methyl ethyl ketone
Mixture is added in the reactor.Then, nitrogen is passed through into reactor 30 minutes to remove the oxygen in monomer mixture
The internal temperature of the reactor is then held in 65 DEG C by gas.After uniform stirring monomer mixture, to the reactor
0.06 parts by weight 2 of middle addition, bis- (2 Methylpropionic acid) dimethyl esters (V601) of 2'- azo be used as initiator, following reaction 4 hours.
The internal temperature of the reactor is increased to 65 DEG C, and the initiator is further added into the reactor.At 70 DEG C
After lower reaction 2 hours, by mixture cooling obtained and methyl ethyl ketone is added into mixture obtained, is thus made
(methyl) acrylic copolymer solution of 25wt%.
Prepare 2~14:(of embodiment methyl) acrylic copolymer preparation
In addition to changing in the monomer mixture other than the type and content of monomer as shown in table 1, according to preparation embodiment 1
In identical method prepare every kind of (methyl) acrylic copolymer.In preparation embodiment 11 and 12, when being aggregated in different
Between section carry out.
Table 1
* in table 1, BA: n-butyl acrylate, MA: methyl acrylate, CHA: cyclohexyl acrylate, IBXA: acrylic acid is different
Norbornene ester, BzA: benzyl acrylate, ACMO: acryloyl morpholine, 4-HBA: acrylic acid 4- hydroxy butyl ester, AA: acrylic acid, DMAEA: the third
Olefin(e) acid dimethylamino ethyl ester
* in table 1, Mw: the weight average molecular weight (unit: g/mol) of acrylic copolymer, Tg: acrylic copolymer
Glass transition temperature (unit: DEG C).
Prepare embodiment 15: the preparation of polyalkylene glycol modified isocyanate curing agent
In round-bottomed flask, having number-average molecular weight (Mn) according to molar ratio (PPG:XDI) 1:2 merging is poly- the third of 400
Glycol (PPG) and xylene diisocyanate (XDI, weight average molecular weight: 188g/mol, TCI Chemicals).Then, by institute
Obtained mixture is heated to 60 DEG C, and is slowly added to conduct according to the dosage of every 1 mole of xylene diisocyanate 0.2wt%
The DBTDL of catalysts, and reaction mixture is made.The reaction mixture is stood 2 hours at 70 DEG C, until from institute
It states and removes the isocyanate groups in reaction mixture.When the amount of remaining xylene diisocyanate reaches 1wt% or more
When few, the reaction is completed, to provide polyalkylene glycol modified isocyanate curing agent.
Prepare embodiment 16-22: the preparation of polyalkylene glycol modified isocyanate curing agent
In addition to using polypropylene glycol and 4,4' methylene bis (isocyanide listed in table 2 according to molar ratio 1:2 (PPG:MDI)
Acid phenenyl ester) (MDI, weight average molecular weight: 250.25g/mol, TCI Chemicals) replace have number-average molecular weight (Mn) be 400
Polypropylene glycol (PPG) and xylene diisocyanate (XDI) and change other than the amount of DBTDL, by with preparation embodiment 15
Identical method prepares every kind of polyalkylene glycol modified isocyanate curing agent.
Table 2
* in table 2, PPG-400: polypropylene glycol (PPG-400D, the Kumho that number-average molecular weight is 400
Petrochemicals), PPG-1000: polypropylene glycol (PPG-1000D, the Kumho of number-average molecular weight 1,000
Petrochemicals), PPG-2000: polypropylene glycol (PPG-2000D, the Kumho of number-average molecular weight 2,000
Petrochemicals), PPG-3000: polypropylene glycol (PPG-3000D, the Kumho of number-average molecular weight 3,000
Petrochemicals)。
The details of component used in embodiment and comparative examples is as follows.
(A) (methyl) acrylic copolymer: (methyl) acrylic copolymer prepared in the preparation embodiment of table 1
(B) curing agent:
(B1) isocyanate curing agent: trimethylolpropane xylene diisocyanate addition product (TD-75, Soken,
Solid content 75wt%)
(B2) metallo-chelate curing agent: M-12AT, solid content 10wt%
(B3) TMPTA: trimethylolpropane trimethacrylate
(B4) PETA: pentaerythritol tetraacrylate
(B5) IRGACURE-184:1- hydroxycyclohexylphenylketone
(B6) TPO:2,4- trimethyl benzoyl diphenyl base phosphine oxide
(B11)~(B18): the polyalkylene glycol modified isocyanate curing agent of table 2
(C) curing catalysts: S promotor (Soken)
(D) silane coupling agent: A-50 (Soken)
(E) antistatic agent: FC-4400 (3M, the U.S.)
(F) agent: MAC-2101 (Soken) is reprocessed
Embodiment 1
(methyl) acrylic copolymer (A1) described in 17 parts by weight and the isocyanates of 0.025 parts by weight is solid
Agent (B1) mixing.In addition, by the curing catalysts (S promotor, Soken) (C) of 0.01 parts by weight, 0.05 parts by weight
The silane coupling agent (A-50, Soken) (D), 0.75 parts by weight the antistatic agent (FC-4400,3M, USA) (E) and
The reprocessing agent (MAC-2101, Soken) (F) of 0.05 parts by weight mixes, and by methyl ethyl ketone with (first described in 4 times
Base) amount of acrylic copolymer weight is added in the mixture, thus prepare the adhesive composition for polarizer.This
Wen Zhong, the content of every kind of component is with solid content definition in addition to the solvents.
Embodiment 2~12
In addition to the kind of type and/or dosage and curing agent according to change (methyl) acrylic copolymer shown in table 3
Other than class and/or dosage (unit: parts by weight), every kind is prepared for the viscous of polarizer by method in the same manner as in Example 1
Mixture composite.
Embodiment 13~20
In addition to the kind of type and/or dosage and curing agent according to change (methyl) acrylic copolymer shown in table 4
Other than class and/or dosage (unit: parts by weight), every kind is prepared for the viscous of polarizer by method in the same manner as in Example 1
Mixture composite.
Comparative examples 1~4
In addition to changing the type of (methyl) acrylic copolymer and/or the type of dosage and curing agent as shown in table 3
And/or other than dosage (unit: parts by weight), every kind of bonding for polarizer is prepared by method in the same manner as in Example 1
Agent composition.
The each component of the described adhesive composition prepared in embodiment and comparative examples is shown in table 3 and 4.
Table 3
Table 4
Following characteristic is had rated to the adhesive composition for being used for polarizer described in embodiment and comparative examples.It is described
Evaluation result is shown in table 5 and 6.
(1) polyvinyl alcohol film: being stretched to three times of its initial length by durability at 60 DEG C, with iodine staining, goes forward side by side one
Step is stretched to 2.5 times in 40 DEG C of boric acid solution, thus prepares polarizer (thickness: 23 μm).Then, by by 80 μ m-thicks
The apparent surface that the tri acetyl cellulose membrane of tri acetyl cellulose membrane and 42 μ m-thicks is bonded to the polarizer respectively is above made
Polarizer.The every kind of adhesive composition prepared in embodiment and comparative examples is coated on the stripping film and at 90 DEG C
Lower drying 4 minutes and remove solvent, the stripping film is then removed, so that adhesive sheet be made.Made bonding sheet is glued
It is affixed on the surface of the tri acetyl cellulose membrane of 42 μm of the polarisation plate thickness, and in 23 DEG C and the constant temperature and humidity condition of 55%RH
It is lower to place 24 hours, the polarizer including bonding film is thus made.
The polarizer is cut into the square having a size of 100mm × 80mm (long × wide) (MD × TD of the polarizer)
Shape.The polarizer cut is attached on alkali-free glass plate (110mm × 90mm, long × wide) via the bonding sheet, thus
The sample for durability measurement is made.Then, by the sample 50 DEG C high pressure sterilization 1000 seconds, be thus formed in the glass
The sample of the polarizer is stacked in glass plate.The sample is placed 500 hours at 85 DEG C or places 500 under 60 DEG C and 95%RH
Hour.The durability of the sample is evaluated by following standard.
Zero: not falling off, do not pull, or do not generate bubble
Δ: small to fall off, small dragging or the generation of micro-bubble, and bubble size is less than 100 μm
×: severe detachment, serious pull generates seriously with bubble, and bubble size is 100 μm or bigger
(2) the every kind of adhesive composition prepared in embodiment and comparative examples warpage: is coated on poly- terephthaldehyde
On sour glycol ester stripping film, and it is 4 minutes dry at 90 DEG C.Bonding film obtained has 25 μm of thickness.By with (1)
In identical method be made with the polarizer of tri acetyl cellulose film being adhered on the apparent surface of the polarizer, and
The bonding film is laminated on the surface of the tri acetyl cellulose membrane of 42 μ m-thicks of the polarizer and at 23 DEG C and 55%
It is placed 24 hours under RH.Polarizer thereon with bonding film is cut into having a size of 210mm × 25mm (long × wide) (polarizer
MD × TD) rectangle.By the polarizer cut via the bonding film be attached to alkali-free glass plate (210mm × 25mm ×
0.5mm, length × width x thickness) on, and high pressure sterilization 1000 seconds at 50 DEG C, the sample for evaluating warpage is thus made.
The sample is placed in 85 DEG C of baking oven 72 hours, and is then placed in atmosphere at room temperature 2 hours.So
Afterwards, the sample is placed on flat surfaces, and one end of the sample is made to be fixed on the flat surfaces, then repeat to survey
Amount is from the flat surfaces to the distance of the sample other end.Record is flat by the warpage for measuring the distance 5 times acquisitions
Warpage of the mean value as the sample.
(3) the every kind of adhesive composition prepared in embodiment and comparative examples dent: is coated on the poly- of 38 μ m-thicks
On ethylene glycol terephthalate stripping film, and it is 4 minutes dry at 90 DEG C, the bonding film of 25 μ m-thicks is thus made.By with
(1) polarisation with the tri acetyl cellulose film being adhered on the apparent surface of the polarizer is made in identical method in
Plate, and the bonding film is laminated at 42 μ m-thicks of the polarizer tri acetyl cellulose membrane surface on and at 23 DEG C and
It is placed 24 hours under 55%RH.Polarizer thereon with bonding film is cut into the size of 50mm × 10mm (long × wide).It is logical
It crosses the polarizer that will be cut to be placed on soda-lime glass plate (thickness: 1mm) and keep the stripping film face-up, then uses adhesive tape
The light polarizing film is fixed on the glass plate and sample is made.
It uses TA instrument (TEXTURE ANALYZER TA.XT Plus, load cell: 5kg, EKO Instruments)
Dent is measured at 25 DEG C.The spherical stainless steel tip (diameter: 1mm) of TA instrument is placed in above the sample stripping film
At the height of 1mm.Under the load of 50gf, by spherical stainless steel tip by described removing membrane pressure 15 seconds, not by the spherical shape
It is removed from stripping film at rust steel tip.Hereafter, the sample is placed 5 minutes.Then, the removing is taken out from the sample
Film, and the dent formed on the bonding film is observed by 3D optical profilometer, the maximum for then recording the pressing label is deep
Degree.
(4) it tan δ: is tested on bonding film and is measured by using the temperature scanning of Anton Paar Physica MCR300
tanδ.With 10 DEG C/min of heating rate from being measured while being warming up to 120 DEG C for 0 DEG C.The bonding film has 600 μ
The thickness of m~1,000 μm.
Table 5
* in table 5, tan δ 1 is tan δ value of the bonding film at 23 DEG C, and when tan δ 2 is 80 DEG C bonding film
Tan δ value.
(1) durability durability: is evaluated by method identical with the durability evaluation of table 5.
(2) warpage: warpage is evaluated by evaluating identical method with the warpage of table 5.
(3) dent: dent is evaluated by evaluating identical method with the dent of table 5, the difference is that from stripping film
After removing the spherical stainless steel tip, period for will being listed in the sample placement table 6.
(4) creep: Fig. 1 is referred to, texture analyser TA.XT PLUS (load cell 5kg, EKO are used
Instruments creep) is evaluated to the bonding film.The every kind of adhesive composition that will be prepared in embodiment and comparative examples
It is coated on polyethylene terephthalate stripping film and 4 minutes dry at 90 DEG C.By with identical method system in (1)
At having the polarizer of tri acetyl cellulose membrane being bonded on the apparent surface of the polarizer, and the bonding film is laminated
It is placed 24 hours on the surface of the tri acetyl cellulose membrane of 42 μ m-thicks of the polarizer and under 23 DEG C and 55%RH, by
The sample 23 with the bonding film 21 (thickness: 25 μm) being attached on a surface of the polarizer 22 is made in this.By sample
It is cut into the rectangle having a size of 100mm × 15mm (long × wide) (MD × TD of polarizer).Then, as shown in Figure 1, by the sample
It is attached on soda-lime glass plate 20, makes the MD of the polarizer perpendicular to a surface of the glass plate 20, and in 15mm
The bonding film is attached on the glass plate in the adhesion area (a × b) of × 15mm.Then, the glass will be attached to
The sample of plate 50 DEG C high pressure sterilization 1000 seconds, and at room temperature place 24 hours.When the sample is pulled by weight W
At 1000 seconds, creep is evaluated from the actuating length of the soda-lime glass plate 20 based on the sample 23.85 DEG C at a temperature of
Creep is measured, the weight W of the measurement creep is 1,500g.
(5) light leakage: by the way that the polarizer comprising bonding film is made with identical method in (1).The polarizer of production is cut
Upper plate is cut into having a size of 150mm × 90mm (MD × TD of polarizer) and lower plate having a size of 90mm × 150mm (polarization of MD × TD
Device) polarizer.Upper plate polarizer is attached to the upper surface of the alkali-free glass plate having a size of 160mm × 100mm (long × wide),
And lower plate polarizer is attached to the lower surface of the alkali-free glass plate.Herein, the upper and lower plates polarizer makes by disposition
The MD of upper plate polarizer is orthogonal with the MD of lower plate polarizer.By the laminated body of the polarizer at 50 DEG C high pressure sterilization 1000
Second, the sample for measuring light leakage is thus made.The sample is placed in 85 DEG C of baking oven 500 hours, then in room temperature
It is lower to place 2 hours.Then, light leakage is measured.After the sample manipulation PLS mode LCD, using luminance test instrument (RISA,
Hiland Co., Ltd.) from the positive brightness of display panel described in 1m elevation carrection.Particularly, the center of the panel is measured
The brightness in regionWith the brightness in each corner for the panel that light leakage occursWithAs shown in Fig. 2, each
The radius of the brightness measurement circle of corner portion is 0.5cm.In Fig. 2,WithIndicate brightness measurement point.
Light leakage degree (Δ L) is quantified according to following formula 4.Δ L value is lower to indicate better light leakage characteristic.It is commented according to following standard
Valence light leakage.
<formula 4>
Δ L=| [(a+b+d+e)/4]/c-1 |
Wherein a, b, d and e indicate the brightness measurement point in Fig. 2WithIt is measured at (high-brightness region)
Brightness value, and c is the middle section in Fig. 2Brightness value at (low brightness area).
Zero: without light leakage, 0≤Δ L≤0.1.
Δ: light bias, 0.1 < Δ L < 0.3.
×: serious light leakage, 0.3≤Δ L
(6) tan δ: tan δ is evaluated by evaluating identical method with the tan δ of table 5.
Table 6
* in table 6, tan δ 1 is tan δ value of the bonding film at 23 DEG C, and tan δ 2 is tan δ of the bonding film at 80 DEG C
Value.
In table 5, it can be seen that polarizer according to the present invention is able to suppress the warpage of polarizer simultaneously with bonding film
With low cup depth, it is thus achieved that inhibit recess in the bonding film and/or fast quick-recovery bonding film processing,
Recess during cutting, packaging and storage in the bonding film due to caused by solid particle.
On the contrary, the bonding film of comparative examples 1~4 and being unsatisfactory for formula 1 and 2, and there is high cup depth.
In table 6, it can be seen that polarizer according to the present invention with bonding film be able to suppress polarizer light leakage and
Warpage, and there is low cup depth, thus enable to inhibit the recess in the bonding film and/or fast quick-recovery bonding film
Processing, cutting, the recess during packaging and storage in the bonding film due to caused by solid particle.
Therefore, the present invention provides a kind of polarizer bonding film, can be in the processing, cutting, packaging of the bonding film
And/or inhibition and/or fast recess of the quick-recovery in the bonding film due to caused by solid particle during storage.
The present invention provides a kind of polarizer bonding film, can be ensured by mitigating the contraction of polarizer at high temperature
Substantially inhibit light leakage.
The present invention provides a kind of polarizer bonding film, shows under the conditions of high temperature or high temperature/high humidity good
Durability, and when being adhered to the metal adhesion body including indium tin oxide (ITO) film, have and inhibits corrosion and can reprocess
Superperformance in terms of property.
It should be understood that without departing from the spirit and scope of the present invention, those skilled in the art can do
Various modifications out change, change and equivalent embodiments.
Claims (23)
1. a kind of bonding film for polarizer, includes: containing with C4-C8(methyl) acrylate of alkyl；With hydroxyl
(methyl) acrylate；And there is C1-C3(methyl) acrylate of alkyl and (methyl) acrylic compounds list with amide groups
(methyl) acrylic copolymer of the monomer mixture of at least one of body, the bonding film meet formula 1 and formula 2:
<formula 1>
0.20≤tanδ2≤0.40
<formula 2>
tanδ2–tanδ1≤0.04
Wherein tan δ 1 is the tan δ value of the bonding film for polarizer at 23 DEG C, and tan δ 2 is the use at 80 DEG C
In the tan δ value of the bonding film of polarizer.
2. the bonding film according to claim 1 for polarizer, wherein tan δ 2-tan δ 1 is in -0.20~0.02
In range.
3. the bonding film according to claim 1 for polarizer, wherein the bonding film meets formula 3:
<formula 3>
tanδ2/tanδ1<1.1
Wherein tan δ 1 is the tan δ value of the bonding film for polarizer at 23 DEG C, and tan δ 2 is the use at 80 DEG C
In the tan δ value of the bonding film of polarizer.
4. the bonding film according to claim 1 for polarizer, wherein described have C4-C8(methyl) propylene of alkyl
Acid esters exists in the monomer mixture with the amount of 40mol%~78mol%.
5. the bonding film according to claim 1 for polarizer, wherein described have C1-C3(methyl) propylene of alkyl
Acid esters and described at least one of (methyl) acrylic monomer with amide groups are deposited with the amount of 10mol%~40mol%
It is in the monomer mixture.
6. the bonding film according to claim 1 for polarizer, wherein described have C1-C3(methyl) propylene of alkyl
Acid esters and described (methyl) acrylic monomer with amide groups are all present in the list with the amount of 10mol%~40mol%
In body mixture.
7. the bonding film according to claim 1 for polarizer, wherein described (methyl) acrylic acid with amide groups
Class monomer includes (methyl) acrylic monomer containing morpholinyl.
8. the bonding film according to claim 1 for polarizer, wherein the monomer mixture, which is free of, has long alkane
(methyl) acrylate of base.
9. the bonding film according to claim 1 for polarizer, wherein the monomer mixture, which further includes, to be had
At least one of (methyl) acrylate of alicyclic group and (methyl) acrylate with aromatic group.
10. the bonding film according to claim 1 for polarizer, wherein the monomer mixture, which further includes, to be had
(methyl) acrylic monomer of tertiary amine group.
11. the bonding film according to claim 1 for polarizer, wherein (methyl) the acrylic copolymer tool
There are -30~-10 DEG C of glass transition temperature and the weight average molecular weight of 500,000~1,500,000g/mol.
12. the bonding film according to claim 1 for polarizer, wherein the bonding film is by including (methyl) third
The adhesive composition of olefin(e) acid analog copolymer and curing agent is formed, and the curing agent includes isocyanate curing agent and metal-chelating
At least one of object curing agent.
13. the bonding film according to claim 12 for polarizer, wherein the isocyanate curing agent includes poly- Asia
At least one of the unmodified isocyanate curing agent of alkyl diol and polyalkylene glycol modified isocyanate curing agent.
14. the bonding film according to claim 12 for polarizer, wherein the polyalkylene glycol is modified isocyanic acid
Ester curing agent includes at least one of the polypropylene glycol that number-average molecular weight is 300g/mol~5,000g/mol and polyethylene glycol.
15. the bonding film according to claim 1 for polarizer, wherein the bonding film is by including (methyl) third
The adhesive composition of olefin(e) acid analog copolymer and curing agent is formed, and the curing agent includes (methyl) acrylic acid of two to six functions
At least one of ester and photoinitiator.
16. the bonding film according to claim 1 for polarizer, wherein the bonding film has 18 μm or smaller recessed
It falls into.
17. a kind of adhesive composition for polarizer, includes: containing with C4-C8(methyl) acrylate of alkyl；Tool
There is (methyl) acrylate of hydroxyl；And there is C1-C3(methyl) acrylate of alkyl and (methyl) third with amide groups
(methyl) acrylic copolymer of the monomer mixture of at least one of alkene acrylic monomer；And curing agent,
The following Expression 1 and formula 2 are wherein met by the bonding film for polarizer that described adhesive composition is formed:
<formula 1>
0.20≤tanδ2≤0.40
<formula 2>
tanδ2-tanδ1≤0.04
Wherein tan δ 1 is the tan δ value of the bonding film for polarizer at 23 DEG C, and tan δ 2 is the use at 80 DEG C
In the tan δ value of the bonding film of polarizer.
18. the adhesive composition according to claim 17 for polarizer, wherein the curing agent includes isocyanic acid
At least one of ester curing agent and metallo-chelate curing agent.
19. the adhesive composition according to claim 18 for polarizer, wherein the isocyanate curing agent packet
Containing in the unmodified isocyanate curing agent of polyalkylene glycol and polyalkylene glycol modified isocyanate curing agent at least it
One.
20. the adhesive composition according to claim 19 for polarizer, wherein the polyalkylene glycol is modified
Isocyanate curing agent include number-average molecular weight be 300g/mol~5,000g/mol polypropylene glycol and polyethylene glycol in extremely
It is one of few.
21. the adhesive composition according to claim 17 for polarizer, wherein the curing agent includes two to six
At least one of (methyl) acrylate of function and photoinitiator.
22. a kind of polarizer, the bonding film comprising being used for polarizer described according to claim 1~any one of 16.
23. a kind of optical display includes polarizer according to claim 22.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0084948 | 2017-07-04 | ||
| KR1020170084948A KR102158871B1 (en) | 2017-07-04 | 2017-07-04 | Adhesive composition for polarizing plate, adhesive film for polarizing plate prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same |
| KR10-2017-0118066 | 2017-09-14 | ||
| KR1020170118066A KR102126048B1 (en) | 2017-09-14 | 2017-09-14 | Adhesive film for polarizing plate, adhesive composition for polarizing plate for the same, polarizing plate comprising the same and optical display apparatus comprising the same |
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| Publication Number | Publication Date |
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| CN109207103A true CN109207103A (en) | 2019-01-15 |
| CN109207103B CN109207103B (en) | 2021-11-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113474164A (en) * | 2019-02-27 | 2021-10-01 | 住友化学株式会社 | Laminate, adhesive composition, and adhesive sheet |
| EP3929262A4 (en) * | 2019-02-19 | 2022-10-19 | Teraoka Seisakusho Co., Ltd. | Acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive tape, and optical device including optical sheet fixed by said pressure-sensitive adhesive tape |
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| CN102858872A (en) * | 2010-04-27 | 2013-01-02 | 日本合成化学工业株式会社 | Acrylic resin solution, acrylic adhesive composition, acrylic adhesive, adhesive sheet, acrylic adhesive for optical member, and optical member with adhesive layer |
| WO2016072197A1 (en) * | 2014-11-04 | 2016-05-12 | 綜研化学株式会社 | Adhesive composition for polarizing plates and polarizing plate having adhesive layer |
| CN105969262A (en) * | 2015-03-11 | 2016-09-28 | 住友化学株式会社 | Adhesive composition, adhesive layer, and optical member with adhesive layer |
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|---|---|---|---|---|
| JP4140736B2 (en) * | 2006-03-15 | 2008-08-27 | 日東電工株式会社 | Adhesive optical film, laminated optical film, and image display device |
| US9605189B2 (en) * | 2013-07-09 | 2017-03-28 | Nitto Denko Corporation | Pressure-sensitive adhesive composition |
| KR101822698B1 (en) * | 2014-11-28 | 2018-01-30 | 삼성에스디아이 주식회사 | Adhesive composition for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same |
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|---|---|---|---|---|
| CN102858872A (en) * | 2010-04-27 | 2013-01-02 | 日本合成化学工业株式会社 | Acrylic resin solution, acrylic adhesive composition, acrylic adhesive, adhesive sheet, acrylic adhesive for optical member, and optical member with adhesive layer |
| WO2016072197A1 (en) * | 2014-11-04 | 2016-05-12 | 綜研化学株式会社 | Adhesive composition for polarizing plates and polarizing plate having adhesive layer |
| CN105969262A (en) * | 2015-03-11 | 2016-09-28 | 住友化学株式会社 | Adhesive composition, adhesive layer, and optical member with adhesive layer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3929262A4 (en) * | 2019-02-19 | 2022-10-19 | Teraoka Seisakusho Co., Ltd. | Acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive tape, and optical device including optical sheet fixed by said pressure-sensitive adhesive tape |
| CN113474164A (en) * | 2019-02-27 | 2021-10-01 | 住友化学株式会社 | Laminate, adhesive composition, and adhesive sheet |
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