CN102732188B - Tackiness composition, tackiness agent and adhesive sheet - Google Patents

Tackiness composition, tackiness agent and adhesive sheet Download PDF

Info

Publication number
CN102732188B
CN102732188B CN201210088874.8A CN201210088874A CN102732188B CN 102732188 B CN102732188 B CN 102732188B CN 201210088874 A CN201210088874 A CN 201210088874A CN 102732188 B CN102732188 B CN 102732188B
Authority
CN
China
Prior art keywords
methyl
acrylic ester
ester polymer
monomer
tackiness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210088874.8A
Other languages
Chinese (zh)
Other versions
CN102732188A (en
Inventor
又野仁
荒井隆行
小泽祐树
所司悟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Publication of CN102732188A publication Critical patent/CN102732188A/en
Application granted granted Critical
Publication of CN102732188B publication Critical patent/CN102732188B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/005—Diaphragms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

There is provided a kind of when being applicable to the optics portion material of polarized light piece etc., the manufacture method of resistance to light leakage and all excellent tackiness composition of weather resistance two side, this tackiness composition, tackiness agent and adhesion thin slice.The feature of this tackiness composition is: be the 1st (methyl) acrylic ester polymer (A) of 50 ten thousand to 300 ten thousand containing weight average molecular weight, weight average molecular weight is the 2nd (methyl) acrylic ester polymer (B) and the glue crosslinking agent (C) of 8000 to 30 ten thousand, described 2nd (methyl) acrylic ester polymer (B) is containing the monomer with the functional group (b1) of reacting with described glue crosslinking agent (C) as constituent, described 1st (methyl) acrylic ester polymer (A), not containing the monomer with the functional group of reacting with described glue crosslinking agent (C) as constituent, or containing as constituent have than described 2nd (methyl) acrylic ester polymer (B) described functional group (b1) with the reactivity of described glue crosslinking agent (C) will be low the monomer of functional group (a1), and described 1st (methyl) acrylic ester polymer (A) and/or described 2nd (methyl) acrylic ester polymer (B), containing the monomer with aromatic nucleus as constituent.

Description

Tackiness composition, tackiness agent and adhesive sheet
Technical field
The present invention relates to tackiness composition, the manufacture method of tackiness composition, tackiness agent (material that tackiness composition glue has joined) and adhesive sheet, particularly, relate to the suitable tackiness composition of the optics for polarized light piece etc., the manufacture method of tackiness composition, tackiness agent and adhesive sheet.
Background technology
Generally, in liquid crystal panel, use the adhering agent layer formed by the property adhesion agent composition of adhesion polarized light piece and polarizer being bonded at glass substrate etc. more.But, the optics of polarized light piece and polarizer etc. is because heat etc. easily produce contraction, there is the contraction that thermal distortion causes, its result, base adhering agent layer stacked on this optics can not follow this contraction, produces the stripping (what is called is floated, and peels off) at interface, the optic axis of optics of stress of the resulting from during contraction of optics departs from, thus produces the problem of light leak (so-called hickie).
As the method preventing this problem, can exemplify, (1) clinging power is high, and, the adhering agent layer that form stability is excellent glues to be paid in the optics of polarized light piece etc., optics self is made to carry out the method suppressed thus, or, the method for the adhering agent layer that stress is little when (2) use the contraction of optics.As the method for (1), as Patent Document 1, the adhering agent layer using storage modulus high is effective.On the other hand, as the method for (2), the adhering agent layer excellent to the stress relaxation rate that the energy of deformation of optics is flexibly corresponding is used to be effective.But in the past, the Games that form the excellent adhering agent layer of such stress relaxation rate closed, be necessary the glue connection density in this adhering agent layer to establish low.So, just have the Strong degree step-down that adhering agent layer is autologous, weather resistance is the problem be deteriorated.
Thus, in patent documentation 2 to 4, not that the glue of adhering agent layer connection density is established low, but by plasticizer, Liquid Paraffin, ammonia ester elastomer etc. makes an addition to acrylic acid or the like tackiness agent, make the adhesion agent composition that obtains moderately soft thus, give stress relaxation rate to adhering agent layer, thus, expect resistance to light leakage and weather resistance.
But add the adhesion agent composition of plasticizer or Liquid Paraffin, the adhering agent layer of formation can ooze out this difficult point along with time plasticizer and Liquid Paraffin.Further, thus, adhesion durability is step-down, and the liquid crystal cells Bei wu of to-be-adhered object dyes, and various problems is worried by people.In addition, add the adhesion agent composition of ammonia ester elastomer, as wanted to maintain intermiscibility, but the addition of ammonia ester elastomer has the upper limit, have the improvement Bu Chong Fen Pour of stress relaxation rate to.Further, in order to heavily stressed relaxation rate, as increased the addition of ammonia ester elastomer, and the intermiscibility meeting step-down of acrylic acid or the like tackiness agent, the problem of white Turbid etc. occurs.So, in technology in the past, optics fundamentally improves the resistance to light leakage of the adhering agent layer having adhesion agent composition to be formed and weather resistance is difficult.
To this, in patent documentation 5, propose to use from comprising (methyl) acrylate 80 to 96 % by weight, in molecule 1 alkene double bond and at least there is the unsaturated monomer 3 to 15 % by weight of aromatic nucleus of 1, and have polar functional base unsaturated monomer 0.1 to 5 % by weight monomer mixture in obtain, weight average molecular weight be 100 ten thousand to 200 ten thousand acrylic resin be the optical thin film with tackiness agent of the adhesion agent composition of principal constituent.
look-ahead technique document
[patent documentation]
[patent documentation 1] JP 2006-235568 publication
[patent documentation 2] Unexamined Patent 5-45517 publication
[patent documentation 3] Unexamined Patent 9-137143 publication
[patent documentation 4] JP 2005-194366 publication
[patent documentation 5] JP 2010-66755 publication
Summary of the invention
[problem of invention]
But use the single acrylic resin of high molecular in the tackiness agent of patent documentation 5, two sides of resistance to light leakage and weather resistance might not be excellent, its performance used for optical part as polarized light piece etc. is insufficient.
The present invention is exactly Given this produce.Object of the present invention is just to provide a kind of when being applicable to the optics of polarized light piece etc., the manufacture method of the excellent tackiness composition of two sides of resistance to light leakage and weather resistance, this tackiness composition, tackiness agent and adhesive sheet.
[solving the means of problem Xie Decision]
Reach to make described order, first, the present invention has for being characterized as one, weight average molecular weight is the 1st (methyl) acrylic ester polymer (A) of 50 ten thousand to 300 ten thousand, weight average molecular weight be 8000 to 30 ten thousand the 2nd (methyl) acrylic ester polymer (B) and glue crosslinking agent (C) and tackiness composition, described 2nd (methyl) acrylic ester polymer (B), the monomer with the functional group (b1) that can react with glue crosslinking agent (C) is contained as constituent, described 1st (methyl) acrylic ester polymer (A), as forming monomer not containing the monomer of functional group with the reaction of reacting with described glue crosslinking agent (C), or contain as forming monomer described functional group (b1) the also reactive functional group (a1) that is low and described glue crosslinking agent (C) had than described 2nd (methyl) acrylic ester polymer (B), and described 1st (methyl) acrylic ester polymer (A) and/or described 2nd (methyl) acrylic ester polymer (B), containing the monomer (technical scheme 1) with aromatic nucleus as constituent.
The tackiness composition of described invention (technical scheme 1) carries out glue and joins the tackiness agent obtained, and has suitable cohesive force and excellent stress relaxation rate.Using this tackiness agent with excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent can be obtained.In addition, the tackiness agent obtained, have the existence of the uniform component of aromatic nucleus, specific refractory power is high, and resistance to light leakage becomes excellent further.
2nd, the invention provides a kind of described tackiness composition (technical scheme 1) glue and join the tackiness agent (technical scheme 2) formed.
The tackiness agent of described invention (technical scheme 2), the break-draw degree in stretching experiment is more than 1000%, and gel ratio is 30 to 90% is preferred (technical scheme 3).
3rd, the present invention is a kind of adhesive sheet with base material and adhering agent layer, it is characterized in that described adhering agent layer, forms (technical scheme 4) by described tackiness agent (technical scheme 2,3).
In described invention (technical scheme 4), described base material preferred light member (technical scheme 5).
4th, the present invention is a kind of tackiness agent sheet, comprises the adhering agent layer that the stripping film of 2 pieces and described stripping film are seized on both sides by the arms, connects thus with the release surface of the stripping film of described 2 pieces, described adhering agent layer is by (technical scheme 6) of described tackiness agent (technical scheme 2,3).
[effect of invention]
In the tackiness agent of tackiness composition glue connection of the present invention, the low-molecular-weight polymkeric substance in the past used as plasticizer is formed the three-dimensional netted structure of chemical glue connection structure, this three-dimensional netted structure, supposition is that the polymkeric substance of multiple high molecular is inserted, in bond between the polymkeric substance of high molecular, thus the plan between the polymkeric substance of formation high molecular is like glue connection structure.Thus, the tackiness agent obtained has suitable cohesive force and excellent stress relaxation rate.Using this tackiness agent with excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., the adhesive sheet that two sides of resistance to light leakage and weather resistance are excellent can be obtained.In addition, the tackiness agent obtained, the composition containing aromatic nucleus is contained equably, and specific refractory power is high, and resistance to light leakage becomes excellent further.
the simple explanation of accompanying drawing
The sectional view of the adhesive sheet of [Fig. 1] the 1st embodiment of the present invention.
The sectional view of the adhesive sheet of [Fig. 2] the 2nd embodiment of the present invention.
[Fig. 3] represents the figure in the mensuration field of the light leak experiment had in the attached polarized light piece of adhering agent layer.。
[Fig. 4] is with the expression figure of the metewand of light leak experiment (visual) in the polarized light piece of adhering agent layer.
embodiments of the present invention
Below, embodiments of the present invention are described.
(tackiness composition)
The tackiness composition of present embodiment, comprise weight average molecular weight (Mw) be 50 ten thousand to 300 ten thousand the 1st (methyl) acrylic ester polymer (A), weight average molecular weight (Mw) be 8000 to 30 ten thousand the 2nd (methyl) acrylic ester polymer (B) and glue crosslinking agent (C), and preferably further containing silane coupling agent (D).In this specification sheets, (methyl) acrylate refers to two sides of acrylate and methacrylic ester.Other similar term too.In addition, " polymkeric substance " is also the concept containing " co-polymer ".
1st (methyl) acrylic ester polymer (A) and/or the 2nd (methyl) acrylic ester polymer (B), contain the monomer with aromatic nucleus as constituent.The tackiness composition of present embodiment, owing to obtaining composition containing having aromatic nucleus, the tackiness agent high refractive index obtained.When particularly the formation monomer of (methyl) acrylic ester polymer (A) and/or the 2nd (methyl) acrylic ester polymer (B) is for having aromatic nucleus, the uniform component containing aromatic nucleus in the tackiness agent obtained, can be made to disperse.
Preferably, at least the 2nd (methyl) acrylic ester polymer (B) is contain the monomer with aromatic nucleus as constituent, particularly preferably, 2nd (methyl) acrylic ester polymer (B), containing the monomer with aromatic nucleus.So, the composition with aromatic nucleus can be estimated by the 2nd (methyl) acrylic ester polymer (B) as contained by constituent, on high refractive index, adding the tackiness agent obtained, make this polymkeric substance (B) and glue crosslinking agent (C) and the framework stabilization of three-dimensional netted structure that formed, the stress relaxation rate of the tackiness agent obtained is high further.Its result, the Games that the composition with aromatic nucleus is contained in polymkeric substance (B) closes, compared with closing with the Games contained in polymkeric substance (A), even if also can play same effect on a small quantity.
Further, there is the composition of aromatic nucleus, beyond described polymkeric substance (A) and/or polymkeric substance (B) contain, as the monomer of the constituent of other polymkeric substance, also can be contained, not as the constituent of polymkeric substance, also can be contained as independently composition.
2nd (methyl) acrylic ester polymer (B), there is the monomer of the functional group (b1) that can react with glue crosslinking agent (C), preferably containing the monomer with aromatic nucleus as constituent as contained as constituent.The monomer with the functional group (b1) that can react with glue crosslinking agent (C) is contained sometimes as constituent,
(1) make the monomer with the functional group (b1) that can react with glue crosslinking agent (C) as constituent, this polymkeric substance (B) is for what contain, the functional group that can react with glue crosslinking agent (C), is essentially only functional group (b1)
(2) preferably have with the reactivity of glue crosslinking agent (C) for meet the functional group (b1) of following formula (I) monomer and, preferably there is the monomer of the functional group (b2) meeting following formula (I) with the reactivity of glue crosslinking agent (C) as constituent.
With the reactivity of glue crosslinking agent (C): functional group (b2) < functional group (b1) ... (I)
That is, in the polymkeric substance (B) of (2), functional group (b1) with the reactivity of glue crosslinking agent (C), reactive high with glue crosslinking agent (C) than functional group (b2).
Described (methyl) acrylic ester polymer (A) or (B) is preferably, the carbon number of alkyl be 1 to 20 (methyl) alkyl acrylate, there is the monomer (monomer containing reactive functional group) and as required of the functional group reacted with glue crosslinking agent (C), the monomer at least one party of polymkeric substance (A) and the polymkeric substance (B) (must Shall) with aromatic nucleus and the co-polymer of other monomer used as required.Further, also preferred the 1st (methyl) acrylic ester polymer (A), as the monomer of component unit containing described reactive functional group.
Carbon number as alkyl is (methyl) alkyl acrylate of 1 to 20, (methyl) methyl acrylate can be exemplified, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl, (methyl) vinylformic acid n-amyl group ester, (methyl) vinylformic acid n-polyhexamethylene, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, (methyl) vinylformic acid n-certain herbaceous plants with big flowers base ester, (methyl) vinylformic acid n-Lauryl Ester, (methyl) myristyl base ester, (methyl) aliphatic acrylate and (methyl) stearyl acrylate base ester etc.These can a kind be used alone, also can two or more use that combines.
On the other hand, as the monomer containing reactive functional group, there is in molecule the monomer (monomer containing hydroxyl) of hydroxyl, have the monomer (monomer containing carboxyl) of carboxyl in molecule, it is preferred for having amino monomer (monomer containing amino) etc. in molecule.
As the monomer containing hydroxyl, (methyl) hydroxyalkyl acrylates etc. of (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 2-hydroxybutyl ester, (methyl) vinylformic acid 3-hydroxybutyl ester and (methyl) vinylformic acid 4-hydroxybutyl ester etc. can be exemplified.These can a kind be used alone, also can two or more use that combines.
As the monomer containing carboxyl, can exemplify, the ethene unsaturated carboxylic acid of vinylformic acid, methacrylic acid, β-crotonic acid, toxilic acid, methylene-succinic acid and citraconic acid etc.These can a kind be used alone, also can two or more use that combines.
As containing amino monomers, can exemplify, (methyl) acrylic-amino ethyl ester and (methyl) n-butyl amino-ethyl ester etc.These can a kind be used alone, also can two or more use that combines.
On the other hand, as the monomer with aromatic nucleus, be preferred to have (methyl) acrylate of aromatic nucleus.As aromatic nucleus, can exemplify phenyl ring, naphthalene nucleus, anthracene nucleus, biphenyl basic ring and fluorenes ring etc., be wherein preferred with phenyl ring.As (methyl) acrylate with phenyl ring, can exemplify, (methyl) benzyl acrylate, (methyl) vinylformic acid benzyl oxygen ethyl ester, (methyl) PhEA, (methyl) vinylformic acid benzene oxygen binaryglycol ester, ethylene oxide sex change (methyl) vinylformic acid p-cresol ester, the acrylic acid nonyl phenolic ester of ethylene oxide sex change (methyl), (methyl) vinylformic acid xenyl oxygen ethyl ester and vinylbenzene etc., wherein (methyl) benzyl acrylate and (methyl) PhEA are preferred.These can a kind be used alone, also can two or more use that combines.
Further, as other monomer described, such as, acrylic acid amides, (methyl) vinylformic acid N of (methyl) acrylate with aliphatics ring of (methyl) cyclohexyl acrylate etc., the non-crosslinking of acrylic acid amides and Methacrylamide etc., N-dimethyl aminoethyl ester and (methyl) vinylformic acid N, (methyl) acrylate of the tertiary amine groups containing non-crosslinking of N-dimethylaminopropyl ester etc., vinyl acetate between to for plastic base ester etc.These can a kind be used alone, also can two or more use that combines.
And, the selection of the monomer of the reactive functional group (a1) used containing the 1st (methyl) acrylic ester polymer (A) and the monomer of reactive functional group (b1) used containing the 2nd (methyl) acrylic ester polymer (B) and the monomer containing reactive functional group (b2), fixed with reactive relation Lai Decision of the glue crosslinking agent (C) used.Following in detail.
At this, the 2nd (methyl) acrylic ester polymer (B), preferably containing the monomer of described reactive functional group (b1), more than 1 quality %, its upper limit be 50 quality % less than.Preferably, containing described reactive functional group (b1) monomer 3 to 40 quality %, particularly preferably 5 to 25 quality %, further preferably containing 10 to 20 quality %.Described scope is in by making the monomer containing reactive functional group (b1), the degree that the glue of the 2nd (methyl) acrylic ester polymer (B) will be made to join becomes good, 1st (methyl) acrylic ester polymer (A) and combination in, the stress relaxation rate of the tackiness agent obtained is excellent.In addition, if the amount containing reactive functional group (b1) monomer is below 1 quality %, the glue connection of the 2nd (methyl) acrylic ester polymer (B) is insufficient, has the weather resistance caused to be possible of step-down.On the other hand, if the amount containing reactive functional group (b1) monomer is more than 50 quality %, excessively, this can cause the laminating adaptability to to-be-adhered object to be the possible of step-down to the glue connection of the 2nd (methyl) acrylic ester polymer (B).Further, when the upper limit of the amount of the monomer containing reactive functional group (b1) is 40 quality %, the resistance to light leakage of the adhesive sheet obtained is more excellent.
The meaning of " being essentially only functional group (b1) " in the polymkeric substance (B) of described (1), refer to other the functional group that reacts with glue crosslinking agent (C) will do not harm functional group (b1) and glue crosslinking agent (C) and reactive degree of admission (this Games closes, and the polymkeric substance (B) of (1) and the polymkeric substance (B) of (2) repeat).Namely, 2nd (methyl) acrylic ester polymer (B), containing have than described functional group (b1) and glue crosslinking agent (C) and reactivity will be low the monomer (monomer containing reactive functional group (b2)) of functional group (b2), as constituent containing particularly preferably promising.Monomer containing reactive functional group (b2) is closed by the Games contained as constituent, as mass ratio, for the monomer containing reactive functional group (b1) amount less than 1/5 amount, the special amount containing less than 1/10 is preferred.
The monomer containing reactive functional group (b2) that 2nd (methyl) acrylic ester polymer (B) has, as mass ratio, as exceed the amount of the monomer containing reactive functional group (b1) 1/5 time, the weather resistance of the adhering agent layer obtained has the possibility of step-down.How out-of-date reactive functional group (b2) in 2nd (methyl) acrylic ester polymer (B) is, in the three-dimensional netted tectosome formed thus, reactive functional group (b2) residue is too many, and the intermiscibility of this three-dimensional netted tectosome and the 1st (methyl) acrylic ester polymer (A) can change (supposition).Its result, Hai Si (Haze) value has the Games of rising to close.In addition, the a large amount of remaining three-dimensional netted tectosome of reactive functional group (b2), the mobility of base the 1st (methyl) acrylic ester polymer (A) inserted in this three-dimensional netted tectosome is by excessively restriction (supposition).Its result, has weather resistance to be that the Games be deteriorated closes.
Further, the tackiness composition of present embodiment closes at the Games containing silane coupling agent (D), silane coupling agent (D), react with reactive functional group (a1) (particularly the carboxyl) of the 1st (methyl) acrylic ester polymer (A), with the occasion of the 1st (methyl) acrylic ester polymer (A) bonding of high molecular, the adherence excellent (supposition) of the tackiness agent obtained and the glass substrate of to-be-adhered object etc., 2nd (methyl) acrylic ester polymer (B) monomer had containing reactive functional group (b2) crosses the occasion of Retained, the alkoxysilyl etc. of silane coupling agent (D), also react with the reactive functional group (b2) (special carboxyl) of the 2nd (methyl) acrylic ester polymer (B), with low-molecular-weight 2nd (methyl) acrylic ester polymer (B) bonding (supposition).Its result, the adherence of the tackiness agent obtained and the glass substrate of to-be-adhered object etc. is deteriorated, and causes the possibility of the weather resistance step-down of adhering agent layer thus.
2nd (methyl) acrylic ester polymer (B), preferably containing monomer 1 to the 40 quality % with described aromatic nucleus, is particularly preferably containing 2 to 20 quality %, is further preferably containing 5 to 15 quality %.When the monomer with aromatic nucleus is more than 1 quality %, the specific refractory power of the tackiness agent obtained is high, and the resistance to light leakage of tackiness agent becomes excellent further.On the other hand, the amount with the monomer of aromatic nucleus is 40 quality % time-out, and be deteriorated with the intermiscibility of the 1st (methyl) acrylic ester polymer (B) etc., Hai Si (Haze) value of the tackiness agent obtained has the possibility of rising.
At this, the carbon number of alkyl be 1 to 20 (methyl) alkyl acrylate with containing there is the monomer of the functional group reacted with glue crosslinking agent (C) and there is the monomer polymerization of aromatic nucleus, the polymerized form of the 2nd (methyl) acrylic ester polymer (B) that obtain, random co-polymer also can, block copolymer also can.
In present embodiment, described the 2nd (methyl) acrylic polymer (B), can a kind be used alone, also can two or more use that combines.Especially, the monomer with aromatic nucleus as constituent the 2nd (methyl) acrylic polymer (B) with containing the monomer that will there is aromatic nucleus as constituent (methyl) acrylic polymer (B) and with being also preferred.Thus, although have the usage quantity step-down of the monomer of aromatic nucleus, but, with using the 2nd (methyl) acrylic polymer (B) all as constituent use the polymkeric substance of the monomer with aromatic nucleus (B) Games close compared with also there is weather resistance and the resistance to light leakage of same degree.This Games closes, and using the monomer with aromatic nucleus as the polymkeric substance (B) of constituent with will not have the preferred composition ratio of monomer as the polymkeric substance (B) of constituent of aromatic nucleus, is mass ratio 40: 60 to 60: 40.
The weight average molecular weight 8000 to 30 ten thousand of the 2nd (methyl) acrylic ester polymer (B), preferably 1 ten thousand to 20 ten thousand, particularly preferably 5 ten thousand to 10 ten thousand.That is, the 2nd (methyl) acrylic ester polymer (B), low-molecular weight polymer composition is formed.Further, the weight average molecular weight in this specification sheets, time the value of polystyrene conversion that measures by gel permeation chromatography (GPC) method.
As the 2nd (methyl) acrylic ester polymer (B) weight average molecular weight as described in scope, distinctive three-dimensional netted formation of structure in the tackiness composition of present embodiment, is conducive to obtaining excellent stress relaxation rate.That is, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) be 8000 less than, good three-dimensional netted structure just can not obtain.On the other hand, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is more than 300,000, intermiscibility step-down, polymkeric substance (A) is just insufficient to the insertion in the three-dimensional netted tectosome of polymkeric substance (B), and weather resistance and reusability will be deteriorated.
1st (methyl) acrylic ester polymer (A), as constituent containing with glue crosslinking agent (C) and the functional group that reacts, or containing than the described functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) and the reactivity of glue crosslinking agent (C) as constituent is the monomer of low functional group (a1), and preferred, as constituent not containing the monomer with the functional group higher with the reactivity of glue crosslinking agent (C) than described functional group (b1).And, 1st (methyl) acrylic ester polymer (A), replace the 2nd (methyl) acrylic ester polymer (B), or also can with the 2nd (methyl) acrylic ester polymer (B) together, as constituent, there is the monomer containing aromatic nucleus.
1st (methyl) acrylic ester polymer (A), can be free of to have and has and glue crosslinking agent (C) and the monomer of functional group that reacts.But, as containing the monomer (containing reactive functional group (a1) monomer) with low reactive functional group (a1) more reactive than the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B), preferred Games is had to close.As contained reactive functional group (a1) in described polymkeric substance (A), the reaction of the 2nd (methyl) acrylic ester polymer (B) and glue crosslinking agent (C) can be promoted, or, silane coupling agent (D) is closed by the Games used, reactive functional group (a1) and this silane coupling agent (D) of the 1st (methyl) acrylic ester polymer (A) react, the adhesion weather resistance of the glass surface to liquid crystal cells etc. of the tackiness agent obtained can be high further, therefore has preferred Games to close.
1st (methyl) acrylic ester polymer (A) closes containing the Games with described reactive functional group (a1) monomer, its amount, usual below 20 quality %, below 15 quality % are preferably, are preferred especially with below 10 quality %.When amount containing reactive functional group (a1) monomer is more than 20 quality %, it is too high that the glass translocation of the 1st (methyl) acrylic ester polymer (A) moves temperature (Tg), and the tackiness agent obtained can not obtain the stress relaxation rate needed.Further, the viewpoint of the reusability imparting of tackiness agent, below the amount 15 quality % of the monomer containing reactive functional group (a1) is preferred.
In addition, compare containing the monomer with reactive functional group (b1) with the 2nd (methyl) acrylic ester polymer (B), the ratio in the 1st (methyl) acrylic ester polymer (A) of what the 1st (methyl) acrylic ester polymer (A) contained the have monomer of reactive functional group (a1) is less than the ratio in the 2nd (methyl) acrylic ester polymer (B) with the monomer of the reactive functional group (b1) contained of the 2nd (methyl) acrylic ester polymer (B) is preferred.Thus, the reactive functional group (a1) that 1st (methyl) acrylic ester polymer (A) contains has suppression to the reaction with glue crosslinking agent (C), and the reactive functional group (b1) that the 2nd (methyl) acrylic ester polymer (B) can be made to contain and glue crosslinking agent (C) carry out certain reaction.
1st (methyl) acrylic ester polymer (A), be not preferred containing the monomer with the functional group equal or more with the reactive functional group (b1) of the reactivity of glue crosslinking agent (C) and the 2nd (methyl) acrylic ester polymer (B) in molecule, if the Games contained closes, there is the amount of the monomer of this functional group in molecule, in polymkeric substance (A), below 1 quality % is that preferably special below 0.5 quality % is preferred.If the amount of this monomer is more than 1 quality %, likely will hinders and answer the 2nd (methyl) acrylic ester polymer (B) of preferential reaction and the reaction of glue crosslinking agent (C).
1st (methyl) acrylic ester polymer (A) Games containing the monomer with described aromatic nucleus closes, its amount, and 1 to 20 quality % is that preferably special 2 to 10 quality % are preferred.The monomer with described aromatic nucleus is the occasion of more than 1 quality %, the tackiness agent high refractive index obtained, and resistance to light leakage might as well.On the other hand, when the amount with the monomer of described aromatic nucleus is 20 quality %, can keep good with the intermiscibility of the composition of polymkeric substance (B) etc.
At this, the carbon number of alkyl is (methyl) alkyl acrylate of 1 to 20, as containing the monomer with reactive functional group, as required, be polymerized with the monomer with aromatic nucleus, the polymerized form of the 1st (methyl) acrylic ester polymer (A) that obtain, for random co-polymer also can, for block copolymer also can.
In present embodiment, described the 1st (methyl) acrylic ester polymer (A), can a kind be used alone, also can two or more use that combines.
The weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is 50 ten thousand to 300 ten thousand, preferably 70 ten thousand to 250 ten thousand, particularly preferably 100 ten thousand to 200 ten thousand.That is, the 1st (methyl) acrylic ester polymer (A) is high-molecular weight polymer composition.
As the 1st (methyl) acrylic ester polymer (A) weight average molecular weight as described in scope, 1st (methyl) acrylic ester polymer (A) of the three-dimensional netted structure formed to the 2nd (methyl) acrylic ester polymer (B) inserts good, by glue connection structure like plans more than 2 molecules of this polymkeric substance (A), polymkeric substance (A), is the state with degree of freedom to a certain degree (supposition) in bond.In addition, polymkeric substance (A), as described in there is the large molecular weight compared, form three-dimensional netted tectosome between polymkeric substance (B), maintain intend like glue connection state, while there is high degree of freedom as molecular chain.Thus, the tackiness agent of formation, have suitable cohesive force and excellent stress relaxation rate, its result, this tackiness agent, resistance to light leakage is excellent simultaneously, and in addition, the adhesion weather resistance under high temperature wet heat condition is abundant, thus can prevent from floating and stripping etc.
At this, the weight average molecular weight as the 1st (methyl) acrylic ester polymer (A) be 500,000 less than, likely make the cohesive force step-down of the tackiness agent obtained, weather resistance and reusability are deteriorated.In addition, if the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is more than 3,000,000, be deteriorated with intermiscibilities such as the 2nd (methyl) acrylic ester polymer (B), Hai Si (Haze) value rises, and is difficult to the stress relaxation rate obtaining needs.
To the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of the 2nd (methyl) acrylic ester polymer (B), 5 to 40 mass parts are preferably, are preferred especially with 10 to 30 mass parts.
Contain in the tackiness agent that the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) tackiness composition obtain with described ratio, 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) is by glue crosslinking agent (C), three-dimensional netted structure is formed, this three-dimensional netted structure, it is the structure that more than the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecule inserts, polymkeric substance (A) is for constructing (supposition) with glue connection like the plan in bond of the state with degree of freedom to a certain degree thus.Thus, the tackiness agent obtained, has suitable cohesive force, and has excellent stress relaxation rate.Thus, the tackiness agent weather resistance obtained and resistance to light leakage excellent.
As glue crosslinking agent (C), preferably exemplify isocyanates glue crosslinking agent, epoxies glue crosslinking agent, ethylenimine class glue crosslinking agent, metal-chelating class glue crosslinking agent etc.
Isocyanates glue crosslinking agent, at least containing polyisocyanate compounds.As polyisocyanate compounds, such as, the ester lopps polymeric polyisocyanate etc. of the aliphatic polymeric isocyanate of the aromatic poly-isocyanate, cyclohexylene diisocyanate etc. of benzyl support vulcabond, methyl diphenylene diisocyanate, p-Xylol group diisocyanate etc., different fluorine and ketone vulcabond, hydrogenation methyl diphenylene diisocyanate etc. and biuret body, the isocyanuric acid ester of these compounds; Further, the affixture etc. of the compound containing low molecule active hydrogen of ethylene glycol, propylene glycol, neopentyl glycol, TriMethylolPropane(TMP) and castor-oil plant wet goods.
As epoxies glue crosslinking agent, may 1 be exemplified, two (the N of 3-, N '-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group m-p-Xylol base diamines, ethylene glycol diglycidyl base ether, 1,6-hexylene glycol diglycidyl ether, TriMethylolPropane(TMP) diglycidyl ether, diglycidylaniline and diglycidyl amine etc.
As ethylenimine class glue crosslinking agent, diphenyl methyl-4 can be exemplified, 4 '-bis-(1-azacyclopropane methane amide), trimethylolpropane tris β-ethylenimine propionic ester, tetramethylol methane three β-ethylenimine propionic ester, toluene 2,4-two (1-azacyclopropane methane amide), triethylene melamine, two different xylylene 1-(2-methyl-aziridinyl propane), three-1-(2-methyl-aziridinyl propane) phosphine and trimethylolpropane tris β-(2-methyl-aziridinyl propane) propionic ester etc.
In metal-chelating class glue crosslinking agent, having atoms metal to be the chelate compound of aluminium, zirconium, titanium, zinc, iron and tin etc., is preferred from performance aluminium chelate compound.As aluminium chelate compound, diisopropoxy aluminium list oleyl alcohol acetylacetate, single aluminum isopropoxide two oleyl alcohol acetylacetate, single aluminum isopropoxide list oleic acid list ethyl acetoacetic acid salt, diisopropoxy aluminium list bay acetylacetate, diisopropoxy aluminium list stearyl acetylacetate and diisopropoxy aluminium list iso stearyl acetylacetates etc. can be exemplified.
The amount of glue crosslinking agent (C), to the crosslinking base with this glue crosslinking agent (C) (such as, isocyanate group) be the reactive functional group (b1) of the 2nd (methyl) acrylic ester polymer (B) (such as, hydroxyl) amount, be generally the amount of 0.05 to 5 equivalent, the preferably amount of 0.1 to 3.5 equivalent, the particularly preferably amount of 0.3 to 1.0 equivalent.As described in the amount of crosslinking base be more than 0.05 equivalent, the gel ratio of the tackiness agent obtained is more than 30%, has sufficient cohesive force, as described in the amount of crosslinking base be 0.1 equivalent, time more than special 0.3 equivalent, the weather resistance of the tackiness agent obtained can become excellent further.On the other hand, as as described in the amount of crosslinking base be below 3.5 equivalents, it is excellent that the tackiness agent obtained obtains reusability, words further as being below 1.0 equivalents, carry out glue connection between polymkeric substance (B) is similar, glue crosslinking agent (C) is consumed thus, thus, can prevent from remaining the polymkeric substance (A) of glue crosslinking agent of the same race between carry out glue connection, or polymkeric substance (A) and polymkeric substance (B) carry out glue connection.
In addition, in present embodiment, as glue crosslinking agent (C), if be consistent occasion with reactive pass of two sides of reactive functional group (b1) and reactive functional group (a1), the glue symbasis of multiple types also can be used together.The control of the three-dimensional netted structure formed from the 2nd (methyl) acrylic ester polymer (B) is easy to viewpoint, such as using isocyanates glue crosslinking agent only, only use the glue crosslinking agent of 1 class to be preferably, only use a kind of glue crosslinking agent to be particularly preferably further.
At this, as glue crosslinking agent (C) with, the monomer containing reactive functional group of (methyl) acrylic ester polymer (A) and (B) and combination, the Games being isocyanates glue crosslinking agent at glue crosslinking agent (C) closes, be preferred as the monomer of the reactive functional group (a1) containing polymkeric substance (A) with the monomer containing carboxyl, as the monomer containing reactive functional group (b1) of polymkeric substance (B), be preferred with the monomer containing hydroxyl or containing amino monomer.
On the other hand, glue crosslinking agent (C) is epoxies glue crosslinking agent, the Games of ethylenimine class glue crosslinking agent or metal-chelating class glue crosslinking agent closes, preferably as the monomer that the monomer of the reactive functional group (a1) containing polymkeric substance (A) is containing hydroxyl, be monomer containing carboxyl as the reactive functional group (b1) containing polymkeric substance (B) containing monomer.
The flexibility of the key formed between glue crosslinking agent (C) and polymkeric substance (B), and the stability of glue connection reaction, further, the reactive base of polymkeric substance (A) and silane coupling agent (D) carry out suitable reaction, to the high contributive viewpoint of the cohesive force of the tackiness agent obtained, so, make glue crosslinking agent (C) for isocyanates glue crosslinking agent, the monomer of the reactive functional group (a1) containing polymkeric substance (A) is made to be monomer containing carboxyl, the monomer of the reactive functional group (b1) containing polymkeric substance (B) is made to be monomer containing hydroxyl, the monomer containing reactive functional group (b2) is not used to be particularly preferably.
The tackiness composition of present embodiment, preferably, further containing silane coupling agent (D).As containing this silane coupling agent (D), 1st (methyl) acrylic ester polymer (A) closes for there being the Games of carboxyl, the carboxyl reaction of the organic reaction base of silane coupling agent (D) etc. and the 1st (methyl) acrylic ester polymer (A), on the other hand, the alkoxysilyl etc. of silane coupling agent (D) plays work to the to-be-adhered object of glass substrate etc.Thus, such as closed by the Games of polarized light piece laminating on liquid-crystalline glasses unit etc., the adherence between tackiness agent and liquid-crystalline glasses unit can be more good.
As this silane coupling agent (D), at least there are in molecule the silicoorganic compound of an alkoxysilyl, good with the intermiscibility of tackiness agent composition, and for there being the material of photopermeability, it is good for being such as essentially transparent material.The addition of such silane coupling agent (D), to the 1st (methyl) acrylic ester polymer (A) 100 mass parts, is that preferably particularly 0.05 to 0.3 mass parts is preferred with 0.01 to 0.5 mass parts.
As the object lesson of silane coupling agent (D), there is vinyltrimethoxy silane, vinyltriethoxysilane, the silicon compound containing polymerizability unsaturated group of methyl allyl acyloxypropyl trimethoxysilane etc.: 3-glycidoxypropyltrime,hoxysilane, the silicon compound with epoxy structure of 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.; 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, the silicon compound containing amino of N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc.; 3-r-chloropropyl trimethoxyl silane, 3-isocyanic ester propyl-triethoxysilicane etc.These, can a kind be used alone, also can two or more use that combines.
The tackiness composition of present embodiment, close at the Games containing the composition with aromatic nucleus as independent component, as this, there is the composition of aromatic nucleus, have except phenyl ring (methyl) acrylate except what enumerate, styrene monomer can also be exemplified, biphenol A diglycidyl ether, fluorene compound class etc.Its amount, to total 100 mass parts of polymkeric substance (A) and polymkeric substance (B), being preferred below 5 mass parts.But, as the composition with aromatic nucleus is closed as the Games that independently composition adds, likely occur to ooze out from tackiness agent, or the phenomenon of density unevenness, so, or to exist in tackiness agent preferably as the constituent of polymkeric substance (A) and/or polymkeric substance (B).
In described tackiness composition, as required, the normally used various additive of acrylic acid or the like tackiness agent can be added, imparting agent of such as adhering, antioxidant, UV light absorber, light stabilizer, softening agent, filling agent, charged preventor, refractive index adjusters etc.
(manufacture method of tackiness composition)
Described tackiness composition, while 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) mix, glue crosslinking agent (C) and silane coupling agent as required (D) can be added at arbitrary section Bands, manufacture therefrom.
As preferred concrete example, (methyl) acrylic ester polymer (A) and (B), they are made with common radical polymerization respectively.The polymerization of (methyl) acrylic ester polymer (A) and (B), can use polymerization starter as required, make with solution polymerization process etc.As polymerization solvent, acetic acid ethyl ester, acetic acid n-butyl ester, i-butyl base ester, toluene, acetone, hexane and methyl ethyl ketone etc. can be exemplified, but also two or more is also used.
As polymerization starter, azo compound can be exemplified, organo-peroxide etc., but also two or more is also used.Azo compound, can 2 be exemplified, 2 '-azobis isobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene 1-nitrile), 2,2 '-azo two (2,4-dimethyl nitrile), 2,2 '-azo two (2,4-dimethyl 4-methoxyl group nitrile), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo two (4-cyanopentanoic acid ester), 2,2 '-azo two (2-hydroxymethyl propionitrile) and 2,2 '-azo two [2-(2-tetrahydroglyoxaline 2-yl) propane] etc.
Organo-peroxide, can exemplify, card acid t-butyl ester (t-Block チ Le パ mono-オ キ シ ネ オ デ カ ノ エ mono-ト) that benzoyl peroxide, t-butyl peroxy benzene methyl, hydrogen phosphide cumene, peroxide two dimethyl isopropyl ester, peroxide two carbonic acid two n-propyl diester, peroxide two carbonic acid two (2-ethoxyethyl group) ester, peroxide are new, peroxide are than the sour t-butyl ester of bar (t-Block チ Le パ mono-オ キ シ PVC バ レ mono-ト), (3,5,5-trimethylammonium cyclopentanone base) superoxide, two propionyl superoxide and diacetyl superoxide etc.
Then, the solution of the polymkeric substance (A) obtained and (B) is mixed, adds dilution solvent.Thereafter, add glue crosslinking agent (C) and silane coupling agent as required (D), fully mix, with solvent dilution, obtain tackiness composition (coating solution).
The diluting solvent used when the dilution of tackiness composition is become coating solution, can exemplify hexane, heptane, the aliphatic hydrocarbon of hexanaphthene etc.; Toluene, the aromatic hydrocarbons of dimethylbenzene etc.; Methylene dichloride, the halohydrocarbon of ethylene dichloride etc.; Methyl alcohol, ethanol, propyl alcohol, butanols, the alcohol of 1-methoxyl group 2-propyl alcohol etc.; Acetone, methyl ethyl ketone, 2-amylalcohol, different fluorine and ketone, the ketone of cyclopentanone etc.; Acetic acid ethyl ester, the ester of acetic acid butyl ester etc., the cellosolve type solvents etc. of ethyl cellosolve etc.
The concentration viscosity of the coating solution of modulation like this, as long as it is just passable to be in the possible scope of coating, has no particular limits, according to circumstances suitable selected.Such as, can be 10 to 40 quality % by the concentration dilution of tackiness composition.Further, when obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as the viscosity that tackiness composition can be coated with, diluting solvent does not add also can.This Games closes, and directly can be coated with tackiness composition.
(tackiness agent)
The tackiness agent of present embodiment is the thing that described tackiness composition glue joins and obtain.The glue connection of described tackiness composition, heat treated can be carried out.Further, this heat treated, can double as the drying treatment of the volatilizations such as the dilution solvent making tackiness composition.
The Games carrying out heat treated closes, and Heating temperature, preferably 50 to 150 DEG C, particularly 70 to 120 DEG C is more preferably.In addition, heat-up time was divided into preferably with 30 seconds to 3, was divided into preferably especially with 50 seconds to 2.Further, after heat treated, be arranged on normal temperature (such as, 23 DEG C, 50%RH) carry out 1 to 2 week left and right the maturation phase for particularly preferably.
By described heat treated (and maturation), the 2nd (methyl) acrylic ester polymer (B) glue joins by glue crosslinking agent (C), and fine and close three-dimensional netted structure is formed (supposition).And, in this three-dimensional netted structure, more than 2 molecules the 1st (methyl) acrylic ester polymer (A) is not direct chemical bond, or must insert along with few chemical bond, thus, this polymkeric substance (A) is in bond, forms glue connection structure (supposition) like intending.In addition, in the 1st (methyl) acrylic ester polymer (A) Games that is carboxyl closes, 1st (methyl) acrylic ester polymer (A) and silane coupling agent (D) react, and the adhesion weather resistance when glass substrate to liquid crystal cells etc. of the tackiness agent obtained adheres to can be able to height.
Break-draw degree in the stretching experiment of the tackiness agent of present embodiment, more than 1000% is that preferably more than 1500% is more preferably, and more than 2000% is particularly preferably, and more than 2500% is further preferably.Further, described break-draw degree represents that the only have adhering agent layer stacked with base material etc. carries out separately the value measured.The tackiness agent of present embodiment has large break-draw degree, so this tackiness agent, shows excellent stress relaxation rate, and two sides of resistance to light leakage and weather resistance are excellent.
Described stretching experiment, specifically, is configured as thickness 500 μm, wide 10mm, and the tackiness agent of long 75mm (wherein, measurement range is 20mm), at 23 DEG C, under the environment of 50%RH, stretches with the speed that 200mm/ divides.
Further, the tackiness agent of present embodiment, when carrying out described stretching experiment, stress during 1000% stretching is below 3N is preferred, and 0.5 to 2.5N is particularly preferably, and in addition, stress during 1500% stretching is 0.8 to 10N is preferred, and particularly 1 to 5N is preferred.
In addition, the tackiness agent of present embodiment, gel ratio is preferably with 30 to 90%, be preferred especially with 40 to 80%, is preferred further with 45 to 75%.The gel ratio of the tackiness agent of present embodiment, namely the degree of glue connection is the words in described scope, the three-dimensional netted structure of the glue connection of the 2nd (methyl) acrylic ester polymer (B) is good, tackiness agent resistance to light leakage and weather resistance two side all excellent.
Further, the gel ratio of tackiness agent is the value of (through later between aging time) during sticky paying.Specifically, be that tackiness composition is coated with at stripping film, after heat treated, at 23 DEG C, under the environment of 50%RH, carry out the gel ratio after keeping in 7 days.This is the gel ratio of tackiness agent, and through front between aging time, its value is variation.Whether from such viewpoint, as closed through not clear Games between aging time, again, at 23 DEG C, after carrying out keeping in 7 days under the environment of 50%RH, gel ratio becomes described scope.
Tackiness agent described above, as used for optical part be preferably, such as, the adhesion of polarized light piece and polarizer, or the adhesion of polarized light piece (polarized light film) and polarizer (phase-contrast film) and glass-based is the most suitable.The adhering agent layer that described tackiness agent is formed, because stress relaxation rate is very excellent, the Games that the dimensional change of to-be-adhered object is large closes, its dimensional change and the stress produced can be absorbed loose by adhering agent layer, so also can not peel off from to-be-adhered object for a long time, simultaneously as described in be used in optics time can prevent in a effective manner light leak.That is, the tackiness agent of present embodiment, resistance to light leakage and weather resistance two side can reach simultaneously.
(adhesive sheet)
As shown in Figure 1, the adhesive sheet 1A of the 1st embodiment, with order from bottom to top, is made up of stacked base material 13 on adhering agent layer 11 folded on the stripping surface layer of stripping film 12, stripping film 12 and adhering agent layer 11.
In addition, shown in Fig. 2, the adhesive sheet 1B of the 2nd embodiment, comprises the stripping film 12a of 2 pieces, 12b, and the adhering agent layer 11 that this stripping film of 2 pieces is seized on both sides by the arms is formed, and the release surface of adhering agent layer 11 and 12a, 12b connects thus.Further, the release surface of the so-called stripping film in this specification sheets comprises in stripping film the face having separability, even if implement the face of lift-off processing and do not implement the face that lift-off processing also can demonstrate separability.
The adhering agent layer 11 no matter which adhesive sheet 1A, 1B seizes on both sides by the arms is all join by described tackiness composition glue the tackiness agent formed to form.
Adhering agent layer 11 thickness, according to adhesive sheet 1A, the application target of 1B carrys out Shi Yi Decision to be determined, be generally 5 to 100 μm, preferably the scope of 10 to 60 μm, such as, as optics, the Games particularly used as the adhering agent layer of polarized light piece closes, and with 10 to 50 μm, is preferred especially with 10 to 30 μm.
As base material 13, be not particularly limited, what the common substrate sheets as adhesive sheet used can use, and can exemplify as required and outside the optics used, with woven or the non-woven fabrics of the fiber of artificial silk, vinylformic acid, polyester etc.; Upper matter paper, glassine paper, impregnation paper, the stationery of White Board etc.; The tinsel of Lv ， Copper etc.; The foam of ammonia ester foaming body, foam polyethylene etc.; The polyester film of polyethylene terephthalate, polybutylene terephthalate, poly-naphthoic acid ethanol ester etc.; Polyurethane film; Polyethylene film; Polypropylene film; The cellulosefilm of triacetyl cellulose etc.; Polyvinyl dichloride film; Polychloride inclined vinyl film; Polyvinyl alcohol film; Ethylene-vinyl acetate base ester co-polymer film; Polystyrene film; Polycarbonate film; Acrylic resin films; Poly-bornylene based resin film; The plastics film of cyclic olefin resins film etc.; These duplexer of more than two kinds etc.Plastics film, the thing that an axial compression is prolonged or two axial compressions are prolonged also can.
As optics, polarized light piece (polarized light film), polarisation, polarizer (phase-contrast film), Shi Jiao Fill Compensation film, luminance brightness-improving film, comparative raising film, liquid crystal polymer film etc. can be exemplified.Wherein, polarized light piece (polarized light film), be easy to shrink, dimensional change is large, and from the viewpoint of resistance to light leakage, the use object as the tackiness agent (described adhering agent layer 11) of present embodiment is very suitable.
The thickness of base material 13, different according to its kind, such as close at the Games of optics, be generally 10 μm to 500 μm, preferably 50 μm to 300 μm.
As stripping film 12, 12a, 12b, polyethylene film can be exemplified, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, polychlorostyrene is for vinyl film, chloroethylenes co-polymer film, pet film, poly-naphthoic acid ethanol ester film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate base ester film, ionic polymer resin film, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylic ester copolymerization thing film, polystyrene film, polycarbonate film, Kapton and fluorine resin film etc.In addition, the glue connection film of these materials also can use.Further, the laminate film of these materials also can use.
In the release surface (face connected with adhering agent layer 11 especially) of described stripping film, preferably implement lift-off processing.The stripper that lift-off processing uses, can exemplify alcohol acids, type siloxane, fluoride compound, unsaturated polyester class, polyolefins and wax class stripper.
The thickness of stripping film 12,12a, 12b has no particular limits, and is generally about 20 to 150 μm.
The manufacture of described adhesive sheet 1A, in stripping film 12 release surface, carries out the coating of the solution (coating solution) containing described tackiness composition, carries out heat treated, after adhering agent layer 11 is formed, and laminated substrate 13 on this adhering agent layer 11.Thereafter, be preferred during maturation is set.
Further, about the condition of heat treated and maturation, as described in.
In addition, the manufacture of described adhesive sheet 1B, it is the release surface of a stripping film 12a (or 12b), the described coating solution containing tackiness composition is coated with, carry out heat treated, after adhering agent layer 11 is formed, on the release surface of stripping film 12b (or 12a) overlaps by this adhering agent layer 11 by another.
As the method for the coating of described coating solution, roller coating method can be exemplified, scraper for coating method, roller coating method, scraper for coating method, press coatings method, gravure coating process etc.
Such as, at this, in the manufacture of the liquid crystal display device be made up of liquid crystal cells and polarized light piece, as the base material 13 of adhesive sheet 1A, use polarized light piece, the stripping film 12 of this adhesive sheet 1A is peeled off, the adhering agent layer 11 and the liquid crystal cells that expose are fitted.
Such as, in addition, about the manufacture of the liquid crystal display device of configuration phase difference plate between liquid crystal cells and polarized light piece, as an example, first, the stripping film 12a (or 12b) of a side of adhesive sheet 1B peels off, and is fitted by the adhering agent layer 11 exposed of adhesive sheet 1B with polarizer.Then, the stripping film 12 of the adhesive sheet 1A of Polarizer is used to peel off as base material 13, the adhering agent layer 11 exposed of adhesive sheet 1A and the laminating of described polarizer.Further, from the adhering agent layer 11 of described adhesive sheet B, another stripping film 12b (or 12a) is peeled off, the adhering agent layer 11 exposed of adhesive sheet B is fitted with liquid crystal cells.
Above adhesive sheet 1A, the stress relaxation rate of the adhering agent layer 11 of 1B is very excellent, such as close at the Games of the adhesion being applicable to polarized light piece, the distortion of polarized light piece and the stress produced can be absorbed loose by adhering agent layer 11, can play excellent resistance to light leakage and high weather resistance (supposition) thus
Embodiment described above is to make the present invention be easier to understand, not forming restriction to the present invention.So each key element that described embodiment is recorded, comprises all design alterations and the equivalent of the scope belonging to technology of the present invention.
Such as, the stripping film 12 of adhesive sheet 1A can omit, and a side of the stripping film 12a in adhesive sheet 1B, 12b also can omit.
[embodiment]
Below, further illustrate the present invention by embodiment etc., scope of the present invention is not limited to these embodiment etc.
(embodiment 1)
1. the modulation of polymkeric substance (A)
To with stirrer, thermometer, also flows water cooler, in the reaction vessel of dripping device and nitrogen ingress pipe, add n-butyl 95.0 mass parts, vinylformic acid 5.0 mass parts, acetic acid ethyl ester 200 mass parts, and 2,2 '-azobis isobutyronitrile 0.08 mass parts.Air nitrogen replacement in described reaction vessel.While stir under this nitrogen atmosphere gas, reaction soln is warming up to 60 DEG C, after reaction in 16 hours, is cooled to room temperature.At this, measured by the following method GPC of the portion of the solution obtained, the polymkeric substance (A) confirming weight average molecular weight 1,500,000 is generated.
2. the modulation of polymkeric substance (B)
To having stirrer, thermometer, also flow water cooler, in the reaction vessel of dripping device and nitrogen ingress pipe, add n-butyl 75.0 mass parts, vinylformic acid 2-hydroxyethyl ester 15.0 mass parts, PhEA 10.0 mass parts, acetic acid ethyl ester 200 mass parts, 2,2 '-azobis isobutyronitrile 0.16 mass parts, and 2 mercapto ethanol 0.3 mass parts.Air nitrogen replacement in described reaction vessel.Stir below at this nitrogen atmosphere gas, while reaction soln is warming up to 70 DEG C, after carrying out reaction in 6 hours, cool to room temperature.At this, the portion of the solution obtained is carried out GPC mensuration by following method, confirm weight average molecular weight be 60,000 polymkeric substance (B) be generated.
3. the modulation of tackiness composition
After polymkeric substance (A) 100 mass parts (solids component scaled value) obtained in described operation (1) and polymkeric substance (B) 15 mass parts (solids component scaled value) obtained in described operation (2) mixing, as glue crosslinking agent (C), add benzyl support vulcabond (TDI class) affixture (Japanese polyurethane Inc., trade(brand)name " can strangle resistance to (コ ロ ネ mono-ト) L ") 1.7 mass parts being equivalent to the TriMethylolPropane(TMP) of 0.6 equivalent of the hydroxyl of polymkeric substance (B).Finally, as silane coupling agent (D), 3-glycidoxypropyltrime,hoxysilane (chemical company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ") 0.2 mass parts is added, and fully stirs, obtains the diluting soln of tackiness composition.
At this, the proportioning of this tackiness composition is as shown in table 1.Further, the meaning of the contracted notation recorded in table 1 etc. is as follows.
[polymkeric substance (A) and (B)]
BA: n-butyl
AA: vinylformic acid
HEA: vinylformic acid 2-hydroxyethyl ester
PhEA: PhEA
BzA: benzyl acrylate
[plasticizer]
Large (ア デ カ サ イ ザ mono-) C-8 of Ah 's jam: trimellitate class plasticizer (three (2-ethylhexyl) trimellitate) (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " large (the ア デ カ サ イ ザ mono-) C-8 of Ah 's jam ")
[glue crosslinking agent (C)]
Isocyanates glue crosslinking agent
Resistance to (コ ロ ネ mono-ト) L can be strangled: benzyl support vulcabond affixture (Japanese polyurethane Inc., trade(brand)name " can strangle resistance to (コ ロ ネ mono-ト) L ") of TriMethylolPropane(TMP)
Its (タ ケ ネ mono-ト) D-110N of Ta Kaina: the Xylene Diisocyanate affixture of TriMethylolPropane(TMP) (Mitsui Chemicals urethane Inc., trade(brand)name " Ta Kaina its (タ ケ ネ mono-ト) D-110N ")
[silane coupling agent (D)]
KBM403:3-glycidoxypropyltrime,hoxysilane (chemical company of SHIN-ETSU HANTOTAI system,
Trade(brand)name " KBM403 ")
KBE9007:3-isocyanic ester propyl-triethoxysilicane (chemical company of SHIN-ETSU HANTOTAI system,
Trade(brand)name " KBE9007 ")
The diluting soln of tackiness composition that knife coater will obtain, be coated on stripping film (the Lin get Ke Inc. one side type siloxane stripper of pet film having been carried out to lift-off processing, SP-PET3811, thickness: 38 μm) lift-off processing face on, this coating will make dried thickness be 25 μm, after this 90 DEG C are carried out 1 minute heat treated, and adhering agent layer is formed.
Then, by what be made up of the polarized light film with disk liquid crystal layer, the polarized light piece that polarized light film and visual angle expand film integration is fitted, adhering agent layer and disk liquid crystal layer is made to connect thus, 23 DEG C, 50%RH carries out maturation in 7 days, obtains the polarized light piece with adhering agent layer.
(embodiment 2 to 16, comparative example 1 to 2)
Except kind and the ratio of each monomer by forming tackiness composition, the kind of glue crosslinking agent and silane coupling agent and addition, the ratio of components of polymkeric substance (A) and polymkeric substance (B) as shown in table 1 such change beyond, same in embodiment 1, manufacture the polarized light piece with adhering agent layer.
At this, described weight average molecular weight (Mw) is the weight average molecular weight of the polystyrene conversion carrying out measuring (GPC mensuration) with gel permeation chromatography (GPC) by following condition.
< condition determination >
GPC determinator: Inc. of Tosoh company, HLC-8020
GPC post (sequentially passing through by following): Inc. of Tosoh company
TSKguardcolumnHXL-H
TSKgelGMHXL(×2)
TSKgelG2000HXL
Measure solvent: tetrahydrofuran (THF)
Measure temperature: 40 DEG C
(experimental example 1) (mensuration of gel ratio)
Polarized light piece is used to change by the making of the manufacture in embodiment or comparative example with the polarized light piece of adhering agent layer, the one side type siloxane stripper of pet film is used to carry out stripping film (the Lin get Ke Inc. of lift-off processing, SP-PET3801, thickness: 38 μm), make adhesive sheet.Specifically, on the adhering agent layer exposed of the constituting body be made up of stripping film/adhering agent layer (thickness: 25 μm) exactly the manufacturing processed in embodiment or comparative example obtained, stacked described stripping film (lift-off processing face will be made to connect with adhering agent layer).Thus, the obtained adhesive sheet be made up of the order of stripping film/adhering agent layer/stripping film.
The adhesive sheet obtained, carries out maturation in 7 days by 23 DEG C under the condition of 50%RH.Thereafter, this adhesive sheet makes the sample of 80mm × 80mm size, and its adhering agent layer polyester net (net size 200) is wrapped, only to the quality of tackiness agent precision balance weighing.Using quality at this moment as M1.
Then, will the tackiness agent in described polyester net be wrapped in, under room temperature (23 DEG C), in acetic acid ethyl ester, carry out 24 h immersion.Thereafter taken out by tackiness agent, temperature 23 DEG C, under the environment of relative humidity 50%, 24 hours air-dry, carries out drying in 12 hours further in the baking oven of 80 DEG C.Only to the quality precision balance weighing of dried tackiness agent.Using quality at this moment as M2.Gel ratio (%) (M2/M1) × 100 calculate.Result is as shown in table 2.
(experimental example 2) (mensuration of optical property)
As mensuration sample, the adhesive sheet (having carried out maturation in 7 days) that the adhesive sheet used when preparing the mensuration with gel ratio is same.About the adhering agent layer of this adhesive sheet, by Hai Si (Haze) instrument (Japanese electricity Se industrial system, NDH2000), Hai Si (Haze) value (%) (also can abbreviation be Hz (%)) is carried out according to JISK7105.Result is as shown in table 2.Further, the scope of preferred Hai Si (Haze) value is 0 to 5%.
(experimental example 3) (light leak experiment)
By the polarized light piece with adhering agent layer obtained in embodiment or comparative example, make the sample of 233mm × 309mm size with cutting device (the super cutter of Di Ye manufacturing company system, PN1-600).Peeled off by stripping film, between the adhering agent layer exposed, sticky pair, in non-alkali glass (Corning Incorporated's system, hawk XG), after this, is carried out 0.5MPa with the made autoclave of the former making of chestnut, at 50 DEG C, carries out 20 points of pressurizations.Further, described laminating, in the table of non-alkali glass, make the polarized light piece with adhering agent layer become polarizing axis to be Niccol cross state (polarizing axis: ∠ 45 °, ∠ 135 °).This state, carries out under 80 DEG C of dry environments placing for 250 hours.After this, at 23 DEG C, carry out under the environment of 50%RH placing for 2 hours, as sample, carry out the evaluation of light leak by method shown below.Result is as shown in table 2.
< light leak is evaluated: Δ L *>
With the MCPD-2000 of great Zhong electronics corporation, to the lightness L in each field shown in the Fig. 3 in described sample *measure, luminosity equation Δ L *, calculate with following formula:
ΔL *＝[(b+c+d+e)/4]-a
But (, a, b, c, d and e, be respectively A field, B field, C field, the lightness in the prespecified measuring point (central part 1 place in each field) in D field and E field), it can be used as light leak.Δ L *value less, light leak is fewer.Further, L *max is the maximum lightness in described whole field.
< light leak is evaluated: visual >
Described sample is arranged on flat head lamp (electric flux industry Inc., HF-SL-A312LC, illumination: 26,000Lux, brightness: 10,000cd) on, (can Ni Ka Minolta Inc. with two-dimensional color luminance meter, CA-2000) carry out a pinch shadow, be transformed into Luminance Distribution image with parsing software (can Ni Ka Minolta Inc., CA-S20w).The Luminance Distribution image of the sample obtained, by the evaluation of metewand shown in Fig. 4.
(experimental example 4) (durability evaluation)
By the polarized light piece with adhering agent layer obtained in embodiment or comparative example, be adjusted to 233mm × 309mm size adjusting with cutting device (the super cutter of Di Ye manufacturing company system, PN1-600).Peeled off by stripping film, between the adhering agent layer exposed, sticky pair, after non-alkali glass (Corning Incorporated's system, hawk XG), at 0.5MPa in the made autoclave of the former making of chestnut, at 50 DEG C, is carried out 20 points of pressurizations.
Thereafter, under putting into the environment of following each durable condition, observe with 10 times of magnifying glasses after 500 hours.Appearance change is benchmark with following.Result is as shown in table 2.
In ◎: 4 limits, no problem
In zero: 4 limit, the position no problem more than from peripheral end to 0.6mm
×: at least 1 limit on 4 limits, peripheral end, to the position of more than 0.6mm, has and floats, and peels off, and foaming, the outward appearance Iso of the tackiness agent of more than the 0.1mm of striped etc. is normal
The durable condition > of <
80 DEG C of dryings
60 DEG C, relative humidity 90%RH
(experimental example 5) (stretching experiment)
One side type siloxane stripper is carried out polyethylene terephthalate stripping film (the Lin get Ke Inc. of lift-off processing, SP-PET3811) lift-off processing face is coated on the tackiness composition of embodiment and comparative example modulation, dried coating thickness is 25 μm, 100 DEG C are carried out heating in 1 minute, form adhering agent layer.The lift-off processing face laminating of the polyethylene terephthalate stripping film (Lin get Ke Inc., SP-PET3801) of its adhering agent layer and Do, obtains adhesive sheet.
Described adhering agent layer is carried out multilayer laminated, makes the aggregate thickness of the adhering agent layer in described adhesive sheet be 500 μm, and only the stripping film on the most top layer of duplexer stays, at 23 DEG C, place 2 weeks under the atmosphere gas of 50%RH.Thereafter, from the adhesive sheet that described adhering agent layer is multilayer laminated cut out 10mm wide × the long sample of 75mm, the stripping film on the most top layer being layered in duplexer is peeled off, sample is installed, make its measurement range be 10mm wide × 20mm is long, 23 DEG C, with tensile testing machine (Ao Rui Inc. under the environment of 50%RH, tensilon) draw speed divided with 200mm/ stretches, when extending 1000%, during 1500% elongation, the stress (N) during 2000% elongation and when 2500% extends measures.Result is as shown in table 2.
[table 1]
Table 1 (Continued)
Table 2
Table 2 (Continued)
Can clearly learn from table 2, what obtain in embodiment has in the polarized light piece of adhering agent layer, even if tackiness agent more than 1000% stretches, its stress is also little, break-draw degree more than 2500%, resistance to light leakage and weather resistance all excellent.On the other hand, what obtain in comparative example has in the polarized light piece of adhering agent layer, the break-draw degree of tackiness agent be 1000% less than, or although tackiness agent can extend 1000%, but its value compared with embodiment of stress now wants large, and resistance to light leakage is low, and weather resistance is insufficient in addition.Further, the tackiness agent in comparative example, all fracture before 1500% extends
industry utilizes possibility
Tackiness composition of the present invention and tackiness agent, optics is suitable for the bonding of such as polarized light piece and polarizer, in addition, and adhesive sheet of the present invention, as the adhesive sheet used for optical part of polarized light piece and polarizer etc., suitable.
the explanation of symbol
1A, 1B... adhesive sheet
11... adhering agent layer
12,12a, 12b... stripping film
13... base material

Claims (6)

1. a tackiness composition, it is characterized in that: be the 2nd (methyl) acrylic ester polymer (B) and the linking agent (C) of 8000 to 30 ten thousand containing weight average molecular weight be 50 ten thousand to 300 ten thousand the 1st (methyl) acrylic ester polymer (A), weight average molecular weight
Described 2nd (methyl) acrylic ester polymer (B) is less than the monomer with the functional group (b1) of reacting with described linking agent (C) as constituent of 50 quality % containing more than 10 quality %,
Described 1st (methyl) acrylic ester polymer (A), not containing the monomer with the functional group of reacting with described linking agent (C) as constituent, or containing the monomer with functional group (a1) that will be low than the described functional group (b1) of described 2nd (methyl) acrylic ester polymer (B) and the reactivity of described linking agent (C) as constituent, and
Described 1st (methyl) acrylic ester polymer (A) and/or described 2nd (methyl) acrylic ester polymer (B), contain the monomer with aromatic nucleus as constituent.
2. the tackiness agent that is cross-linked of the tackiness composition of claim 1.
3. tackiness agent according to claim 2, is characterized in that: the extension at break degree of the stretching experiment of described tackiness agent is more than 1000%, and gel fraction is 30 to 90%.
4. an adhesion thin slice, has base material and adhering agent layer, it is characterized in that:
Described adhering agent layer, is formed by the tackiness agent of claim 2 or 3.
5. adhesion thin slice according to claim 4, is characterized in that: described base material is optics.
6. an adhesion thin slice, comprising:
The peeling sheet of 2 pieces, and
By the adhering agent layer that described peeling sheet is seized on both sides by the arms,
Thus, connect with the release surface of the peeling sheet of described 2 pieces;
It is characterized in that: described adhering agent layer is formed by the tackiness agent of claim 2 or 3.
CN201210088874.8A 2011-03-31 2012-03-29 Tackiness composition, tackiness agent and adhesive sheet Active CN102732188B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-079022 2011-03-31
JP2011079022A JP5595321B2 (en) 2011-03-31 2011-03-31 Adhesive composition, adhesive and adhesive sheet

Publications (2)

Publication Number Publication Date
CN102732188A CN102732188A (en) 2012-10-17
CN102732188B true CN102732188B (en) 2016-01-06

Family

ID=46988505

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210088874.8A Active CN102732188B (en) 2011-03-31 2012-03-29 Tackiness composition, tackiness agent and adhesive sheet

Country Status (4)

Country Link
JP (1) JP5595321B2 (en)
KR (1) KR101899382B1 (en)
CN (1) CN102732188B (en)
TW (1) TWI546364B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5611880B2 (en) * 2011-03-31 2014-10-22 リンテック株式会社 Adhesive and adhesive sheet
JP5602670B2 (en) * 2011-03-31 2014-10-08 リンテック株式会社 Adhesive and adhesive sheet
EP3088924B1 (en) * 2013-12-27 2018-09-19 Zeon Corporation Optical laminate and surface light source device
CN108384505B (en) * 2015-03-20 2020-10-30 东洋油墨Sc控股株式会社 Adhesive and adhesive tape
KR102047288B1 (en) * 2015-12-10 2019-11-21 주식회사 엘지화학 Pressure sensitive adhesive composition
KR102024256B1 (en) 2016-09-23 2019-11-04 주식회사 엘지화학 Pressure sensitive adhsive composition
JP6307189B2 (en) * 2017-03-02 2018-04-04 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet
JP2022179185A (en) * 2021-05-21 2022-12-02 日東電工株式会社 Adhesive sheet, optical laminate and image display device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1174224A (en) * 1996-07-18 1998-02-25 日东电工株式会社 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheets
CN1570007A (en) * 2003-04-30 2005-01-26 东洋油墨制造株式会社 Adhesive and optical parts using the same
CN1958660A (en) * 2005-11-04 2007-05-09 住友化学株式会社 Acrylic acid resin composition and adhesive
CN101313043A (en) * 2005-11-21 2008-11-26 综研化学株式会社 Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3533589B2 (en) * 1997-04-09 2004-05-31 綜研化学株式会社 Pressure-sensitive adhesive composition for polarizing plate and polarizing plate
JP2000109771A (en) * 1998-10-07 2000-04-18 Lintec Corp Adhesive sheet
JP4072309B2 (en) * 2000-10-13 2008-04-09 日本カーバイド工業株式会社 Adhesive composition for polarizing film and polarizing film
KR100668943B1 (en) * 2004-04-23 2007-01-12 주식회사 엘지화학 Acrylic Pressure-Sensitive Adhesive Composition for the Polarizing Film
JPWO2005111167A1 (en) * 2004-05-19 2008-03-27 綜研化学株式会社 Adhesive composition
JP4839745B2 (en) * 2004-09-17 2011-12-21 住友化学株式会社 Optical laminate
KR100948778B1 (en) * 2007-01-23 2010-03-24 주식회사 엘지화학 Optically Compensated Acrylic Pressure-Sensitive Adhesive Composition, Polarizing Plate and Liquid Crystal Display Device containing the same
KR101019064B1 (en) * 2008-01-14 2011-03-07 주식회사 엘지화학 Acrylic Pressure-Sensitive Adhesive Composition
JP5379409B2 (en) * 2008-02-15 2013-12-25 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP5243197B2 (en) * 2008-11-18 2013-07-24 日東電工株式会社 Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, and image display device
JP5595034B2 (en) * 2009-12-28 2014-09-24 リンテック株式会社 Adhesive composition, adhesive and adhesive sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1174224A (en) * 1996-07-18 1998-02-25 日东电工株式会社 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheets
CN1570007A (en) * 2003-04-30 2005-01-26 东洋油墨制造株式会社 Adhesive and optical parts using the same
CN1958660A (en) * 2005-11-04 2007-05-09 住友化学株式会社 Acrylic acid resin composition and adhesive
CN101313043A (en) * 2005-11-21 2008-11-26 综研化学株式会社 Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition

Also Published As

Publication number Publication date
JP5595321B2 (en) 2014-09-24
KR20120112100A (en) 2012-10-11
KR101899382B1 (en) 2018-09-17
CN102732188A (en) 2012-10-17
JP2012214547A (en) 2012-11-08
TWI546364B (en) 2016-08-21
TW201241140A (en) 2012-10-16

Similar Documents

Publication Publication Date Title
CN102732188B (en) Tackiness composition, tackiness agent and adhesive sheet
CN102108272B (en) Pressure sensitive adhesive composition, pressure sensitive adhesive and pressure sensitive adhesive sheet
TWI672347B (en) Adhesive composition for optical film, adhesive layer for optical film, optical film with adhesive layer, and image display device
US9487681B2 (en) Pressure-sensitive adhesive compositions, polarizers and liquid crystal displays comprising the same
CN102888201B (en) Adherence composition, sticker and adhesive sheet
TWI518158B (en) Adhesive composition for optical film, adhesive layer for optical film, adhesive type optical film and image display device
CN102888200A (en) Adhesive and adhesive sheet
CN102373028B (en) Pressure-sensitive-adhesive composition, pressure sensitive adhesive and pressure sensitive adhesion sheet
CN102373027B (en) Pressure-sensitive-adhesive composition, pressure sensitive adhesive and pressure sensitive adhesion sheet
CN101531873A (en) Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display
CN104981529A (en) Adhesive composition for acrylic-based or cycloolefin-based polarizing film, adhesive layer, acrylic-based or cycloolefin-based polarizing film having adhesive layer, and image formation device
CN102618183A (en) Adhesive sheet and optical film and optical laminating body having the adhesive sheet
CN103374274A (en) Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
CN103980820A (en) Pressure-sensitive adhesion composition, pressure-sensitive adhesive, and pressure-sensitive adhesion sheet
CN102888202B (en) Tackiness composition, tackiness agent and adhesive sheet
TW201821569A (en) Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device
KR101914458B1 (en) Adhesive composition, adhesive and adhesive sheet
TW201821576A (en) Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device
CN102888203B (en) Tackiness composition, tackiness agent and adhesive sheet
CN103146323A (en) An adhesive and adhesion sheet
CN105647443A (en) Adhesive composition for polarizing plate, polarizing plate including the same, and optical display including the same
CN102732189A (en) Adhesive and adhesive sheet
TW201710434A (en) Surface-protective film for polarizing plate
CN106795415B (en) Adhesive phase, polarizing film and laminated body with adhesive phase
CN102732187A (en) Adhesive and adhesive sheet

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant