CN102888203B - Tackiness composition, tackiness agent and adhesive sheet - Google Patents
Tackiness composition, tackiness agent and adhesive sheet Download PDFInfo
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- CN102888203B CN102888203B CN201210224025.0A CN201210224025A CN102888203B CN 102888203 B CN102888203 B CN 102888203B CN 201210224025 A CN201210224025 A CN 201210224025A CN 102888203 B CN102888203 B CN 102888203B
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/005—Diaphragms
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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
- 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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
There is provided a kind of when being applicable to the optics of polarization plate etc., stress relaxation rate is excellent and while can preventing light leak, and weather resistance is also excellent, and reusability is also good further tackiness composition, tackiness agent and adhesive sheet.Tackiness composition of the present invention contains, the 2nd (methyl) acrylic ester polymer (B) and linking agent (C) that the 1st (methyl) acrylic ester polymer (A) that weight average molecular weight is 500,000 ~ 3,000,000, weight average molecular weight are 8000 ~ 300,000.1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), separately in fact not containing acidic groups, and contain hydroxyl monomer as the monomer unit forming described polymkeric substance.The hydroxyl monomer that 1st (methyl) acrylic ester polymer (A) contains and the hydroxyl monomer that the 2nd (methyl) acrylic ester polymer (B) contains are one species.Be 1.0 ~ 40 to the mol ratio of the hydroxyl contained in the 2nd (methyl) acrylic ester polymer (B) of the hydroxyl contained in the 1st (methyl) acrylic ester polymer (A).
Description
Technical field
The present invention relates to tackiness composition, tackiness agent (material that tackiness composition is crosslinked) and adhesive sheet, particularly, relate to as well suited tackiness composition, tackiness agent and adhesive sheet such as the optics of polarized light piece etc.
Background technology
In general, in liquid crystal panel, polarized light piece and polarizer are adhered to the glass substrate of liquid crystal cells etc. upper bonding in, use the adhering agent layer formed from adhesion agent composition more.But, the optics of polarized light piece and polarizer etc. can be easy to shrink by heat etc., its result, adhering agent layer stacked on described optics is difficult to follow its contraction, thus peel off at interface that (what is called is floated, peel off), departing from of optic axis of the optics of stress cause when can there is the contraction of optics and produce light leak (so-called hickie).
As the method prevented it, (1) can be exemplified clinging power is high, and, the adhering agent layer that form stability is excellent fits in the optics of polarized light piece etc., thus make the method that the contraction self of optics suppresses, or (2) use the adhering agent layer method that the stress during contraction of optics is little.As the method for (1), the high adhering agent layer of the such storage modulus using patent documentation 1 to record is effective.On the other hand, as the method for (2), the adhering agent layer that can carry out soft corresponding stress relaxation rate excellent to the distortion of optics is used to be effective.
To the method using (2), in patent documentation 2, describe a kind of polarized light piece tackiness agent, it is for be comprised by one: (A) (methyl) alkyl acrylate and have the co-polymer of polymerizable monomer 0.5-20 % by weight of the functionality to linking agent, and its weight average molecular weight is high molecular (methyl) the acrylic copolymers 100 weight portion of more than 1,000,000; (B) lower molecular weight (methyl) acrylic acid or the like (being total to) the polymkeric substance 20-200 weight portion of weight average molecular weight less than 30,000, the functional group that (C) can form crosslinked configuration has at least the multi-functional compounds 0.005-5 weight portion of 2 to form in molecule.Functional group's partition ratio that [functional group of lower molecular weight (methyl) acrylic acid or the like (being total to) polymkeric substance]/[functional group of high molecular (methyl) acrylic copolymers] represents is in the scope of 0-15 % by weight.
Equally, to the enforcement of the method for described (2), at patent documentation 3, describe a kind of optics adhesion agent composition, its by weight average molecular weight be 800,000-200 ten thousand (methyl) acrylic ester copolymerization thing (a) 100 mass parts and weight average molecular weight be less than 50,000 the acrylic ester copolymerization thing mixture (A) that forms of (methyl) acrylic ester copolymerization thing (b) 20-100 mass parts and linking agent (B) form, and there is described co-polymer (a) comprising the monomer unit of the functional group high with the reactivity of linking agent (B), and described co-polymer (b) comprises the monomer unit of the functional group lower than the functional group of described co-polymer (a) with the reactivity of linking agent (B).
[patent documentation]
[patent documentation 1] JP 2006-235568 publication
[patent documentation 2] patent No. 3533589 publication
[patent documentation 3] JP 2009-108122 publication
Patent documentation 2, tackiness agent disclosed in 3, by making (methyl) acrylic copolymers of high molecular preferentially be cross-linked, thus obtains stress relaxation rate.Such as, but the poor durability of described tackiness agent, under wet heat condition, adhesion interface is peeled off.Stress relaxation rate also not fully, when being used in the optics of polarized light piece etc., has the occasion that light leak occurs in addition.Further, attach tendency that is rear or clinging power rising in time, reusability is insufficient.
Summary of the invention
The present invention, in view of such actual state forms.Object of the present invention is just to provide a kind of when being applicable to the optics of polarized light piece etc., and stress relaxation rate is excellent, and while can preventing light leak, weather resistance is also excellent, tackiness composition, tackiness agent and adhesive sheet that further reusability is also good.
Reach to make described object, 1st, the invention provides a kind of tackiness composition, comprise the 1st (methyl) acrylic ester polymer (A) that weight average molecular weight is 500,000-300 ten thousand, weight average molecular weight is the 2nd (methyl) acrylic ester polymer (B) of 8000-30 ten thousand and the tackiness composition of linking agent (C), it is characterized in that: described 1st (methyl) acrylic ester polymer (A) and described 2nd (methyl) acrylic ester polymer (B), respectively, in fact not containing acidic groups, and contain hydroxyl monomer as the formation monomer unit of described polymkeric substance, the hydroxyl monomer that described 1st (methyl) acrylic ester polymer (A) contains, the hydroxyl monomer contained with described 2nd (methyl) acrylic ester polymer (B) is one species, to the hydroxyl that described 1st (methyl) acrylic ester polymer (A) contains, the mol ratio of the hydroxyl that described 2nd (methyl) acrylic ester polymer (B) contains, for 1.0-40 (invention 1).
The tackiness composition of described invention (invention 1) is carried out crosslinked and tackiness agent that is that obtain, suitable cohesive force and excellent stress relaxation rate can be played.Have the tackiness agent of this excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., two sides that can obtain resistance to light leakage and weather resistance are excellent, the adhesive sheet that further reusability is also good.In addition, each polymkeric substance of described tackiness composition, owing to substantially not containing acidic groups, to-be-adhered object is the occasion that metal is formed or the occasion containing metal, and described corrosion of metal can be suppressed.
In described invention (invention 1), described 2nd (methyl) acrylic ester polymer (B), as the formation monomer unit of this polymkeric substance, preferably containing described hydroxyl monomer is 10-40 quality % (invention 2).
Described invention (invention 1,2) in, to described 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described 2nd (methyl) acrylic ester polymer (B), is preferably 5-50 mass parts (invention 3).
In described invention (invention 1-3), described 1st (methyl) acrylic ester polymer (A) and described 2nd (methyl) acrylic ester polymer (B), beyond preferred hydroxyl-removal, in fact not containing with described linking agent (C), there is reactive functional group (inventing 4).
In described invention (invention 1-4), described linking agent (C), is preferably isocyanates linking agent (invention 5).
In described invention (invention 5), the amount of described isocyanates linking agent, the amount of isocyanate group to the described hydroxyl that described 2nd (methyl) acrylic ester polymer (B) contains for described isocyanates linking agent is the amount (invention 6) of 0.1-3.5 equivalent.
2nd, the present invention, provides a kind of tackiness agent (invention 7) crosslinked by described tackiness composition (invention 1-6).
3rd, the present invention, for having the adhesive sheet of base material and adhering agent layer, is characterized in that: described adhering agent layer is made up of (invention 8) described tackiness agent (invention 7).
In described invention (invention 8), described base material, preferred light member (invention 9).
4th, the invention provides a kind of adhesive sheet, it is made up of 2 pieces of stripping films and the adhesive layer of being seized on both sides by the arms by the stripping film of described 2 pieces, adhering agent layer connects with the release surface of 2 pieces of stripping films thus, it is characterized in that: described adhering agent layer is made up of (invention 10) described tackiness agent (invention 7).
[effect of invention]
In the tackiness agent that tackiness composition of the present invention is cross-linked, the low-molecular-weight polymkeric substance in the past used as plasticizer is preferentially cross-linked, the three-dimensional netted structure of described low-molecular-weight polymer formation chemically crosslinked, in this three-dimensional netted structure, the polymkeric substance of multiple high molecular is had to insert, the polymer of high molecular is in bond, forms the crosslinked configuration (supposition) like intending between the polymer of high molecular thus.Thus, the tackiness agent obtained, can play suitable cohesive force and excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., while effectively preventing light leak, weather resistance is also excellent, and further reusability is also good.In addition, each polymkeric substance of tackiness composition of the present invention, in fact not containing acidic groups, so the occasion that is made up of metal of to-be-adhered object or the occasion containing metal, can suppress described metallic corrosion.
Accompanying drawing explanation
Fig. 1 is the sectional view of the adhesive sheet of the 1st embodiment of the present invention.
Fig. 2 is the sectional view of the adhesive sheet of the 2nd embodiment of the present invention.
Fig. 3 represents that (visual) of the light leak experiment had in the polarized light piece of adhering agent layer evaluates the figure in base Huaihe River.
there is embodiment
Below, embodiments of the present invention are described.
(tackiness composition)
The tackiness composition of present embodiment, be the 1st (methyl) acrylic ester polymer (A) of 500,000-300 ten thousand, the 2nd (methyl) acrylic ester polymer (B) of weight average molecular weight (Mw) and 8000-30 ten thousand and linking agent (C) containing weight average molecular weight (Mw), preferably further containing silane coupling agent (D).In addition, in this manual, (methyl) acrylate, has the meaning of two sides of acrylate and methacrylic ester.Other similar term too.In addition, the concept also containing " co-polymer " in " polymkeric substance ".
1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), respectively, in fact not containing acidic groups, and described polymkeric substance contains hydroxyl monomer (monomer containing hydroxyl in molecule) as the monomer unit formed, preferably, the carbon number of alkyl be (methyl) alkyl acrylate of 1-20, hydroxyl monomer and use as required not containing the co-polymer with other the monomer of the functional group of linking agent (C) responding property.
As acidic groups, mainly exemplify carboxyl, other, can exemplify sulfonic group and phosphate etc.1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) be not in fact containing acidic groups, to-be-adhered object be metal form occasion (such as, to-be-adhered object is the occasion of the electrode that tin indium oxide (ITO) is formed) or containing metal occasion (such as, to-be-adhered object contains the occasion of wire netting), described metallic corrosion can be inhibited.
At this, so-called " in fact not containing acidic groups ", refers to completely not containing outside acidic groups, also comprises thus permissible degree small to the degree of corrosion of metal.Specifically, be the component unit as polymkeric substance (A) or (B), containing the amount of acidic groups monomer, be generally 1 quality % less than, preferably 0.5 quality % less than, particularly preferably 0.1 quality % less than.
Carbon number as alkyl is (methyl) alkyl acrylate of 1-20, (methyl) methyl acrylate can be exemplified, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butylacrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid n-hexyl ester, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, (methyl) vinylformic acid positive certain herbaceous plants with big flowers base ester, (methyl) vinylformic acid dodecyl ester, (methyl) myristyl base ester, (methyl) aliphatic acrylate and (methyl) stearyl acrylate base ester etc.They can be suitable for separately, but also two or more combinationally uses.
As hydroxyl monomer, (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.They can be suitable for separately, but also two or more combinationally uses.
In the tackiness composition of present embodiment, the hydroxyl monomer that 1st (methyl) acrylic ester polymer (A) contains and the hydroxyl monomer that the 2nd (methyl) acrylic ester polymer (B) contains are one species, and, be 1.0-40 to the mol ratio of the hydroxyl that the 2nd (methyl) acrylic ester polymer (B) of the hydroxyl that the 1st (methyl) acrylic ester polymer (A) contains contains, preferred 3-30, particularly preferably 5-20.
In addition, described mol ratio, in other words, refers to mole number of the hydroxyl to polymkeric substance (A) origin in tackiness composition, the mole number object ratio of the hydroxyl of polymkeric substance (B) origin.Such as, in tackiness composition, when polymkeric substance (A) 100 mass parts and polymkeric substance (B) 20 mass parts coordinate, represent the mole number object ratio of the hydroxyl of described use level.In addition, " one species " in this specification sheets, not only refers to same hydroxyl monomer, the occasion existed in same polymkeric substance, also refers to the hydroxyl monomer same with the reactive essence of linking agent (C).
As described in, for the hydroxyl of the hydroxyl monomer origin of same, 2nd (methyl) acrylic ester polymer (B) is compared with the 1st (methyl) acrylic ester polymer (A), containing time above with amount, when described tackiness composition is cross-linked, 2nd (methyl) acrylic ester polymer (B) (low-molecular weight polymer) and linking agent (C) preferential reaction, form three-dimensional netted structure (supposition) between linking agent (C).Thus, this three-dimensional netted structure, it is more than the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecule, not with direct chemical bond or only have few chemical bond with and insert, polymer (A) is in the state of degree of freedom to a certain degree and in bond, thus forms the crosslinked configuration (suppositions) like intending (structure so inferred is hereinafter also referred to " constructing X ").1st (methyl) acrylic ester polymer (A), the amount of hydroxyl is less, inserts well so be taken into account in described three-dimensional netted structure.There is the tackiness agent of described structure X, suitable cohesive force and excellent stress relaxation rate can be played.There is the tackiness agent of so excellent stress relaxation rate, when being applicable to the optics of polarized light piece etc., while resistance to light leakage is excellent, also can prevent float and stripping etc. under the conditions such as weather resistance is also excellent, damp and hot.In addition, even if the 2nd (methyl) acrylic ester polymer (B) and the 1st (methyl) acrylic ester polymer (A) occasion containing the hydroxyl with amount, compared with the polymkeric substance (A) of high molecular, the density of the hydroxyl of low-molecular-weight polymkeric substance (B) is high, that cause due to structure also can become few with difficulty that the is contact of linking agent (C), polymkeric substance (B) and linking agent (C) preferentially react thus.Further, in described structure X, due to the uncrosslinked low molecular weight compositions etc. not used for imparting stress relaxation rate, would not occur so become oozing out etc. of the low molecular weight compositions of problem in the tackiness agent of stress relaxation rate type in the past, its result, from the tackiness agent that the tackiness composition of present embodiment obtains, reusability is also excellent.
2nd (methyl) acrylic ester polymer (B), as formation monomer unit, preferably containing hydroxyl monomer is 10-40 quality %, and particularly containing 10-30 quality % is preferably, and further 12-20 quality % is containing preferably promising.Hydroxyl monomer within the scope of this by the words contained, the crosslinked degree of the 2nd (methyl) acrylic ester polymer (B) will be good, with the combination of the 1st (methyl) acrylic ester polymer (A), the stress relaxation rate of tackiness agent will more effectively improve.As hydroxyl monomer amount 10 quality % less than time, the 2nd (methyl) acrylic ester polymer (B's) is crosslinked insufficient, and solidifying point rate of handing over is low, has the possibility that weather resistance is deteriorated.On the other hand, if the amount of hydroxyl monomer is more than 40 quality %, 2nd (methyl) acrylic ester polymer (B's) is excessively crosslinked, stress relaxation rate just has the possibility of variation, and after cross-linking, hydroxyl is remaining, and the weather resistance particularly under wet heat condition is deteriorated.In addition, the upper limit of the amount of hydroxyl monomer is as fixed on 30 quality %, and the resistance to light leakage of the adhesive sheet obtained will be excellent further.
In addition, the preferred amount of the hydroxyl monomer in the 1st (methyl) acrylic ester polymer (A), by the amount of hydroxyl monomer in described 2nd (methyl) acrylic ester polymer (B) and the mol ratio of above-mentioned hydroxyl, automatically determined.
As other monomer described, (methyl) acrylate with aliphatics ring of (methyl) cyclohexyl acrylate etc. can be exemplified; There is (methyl) acrylate having aromatic ring of (methyl) phenylethyl etc.; The acrylamide of the non-crosslinked of acrylamide and Methacrylamide etc.; (methyl) vinylformic acid N, N-dimethyl aminoethyl ester and (methyl) vinylformic acid N, (methyl) acrylate with tertiary amine groups of the non-crosslinked of N-dimethylaminopropyl ester etc., vinyl-acetic ester and vinylbenzene etc.They can be suitable for separately, but also two or more combinationally uses.
Among other monomer described, (methyl) vinylformic acid N, N-dimethyl aminoethyl ester and (methyl) vinylformic acid N, (methyl) acrylate with tertiary amine groups of the non-crosslinked of N-dimethylaminopropyl ester etc., particularly (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, there is the effect of catalyst promoting that the reaction of the hydroxyl in polymkeric substance and linking agent (C) has promotion, so in the 2nd (methyl) acrylic ester polymer (B), as the monomer unit of the formation of described polymkeric substance, containing also can.
This occasion, the amount with (methyl) acrylate of tertiary amine groups of the described non-crosslinked in the 2nd (methyl) acrylic ester polymer (B) is that preferably particularly 1-5 quality % is preferred with 0.1-10 quality %.
At this, really formed to make described structure X, 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), beyond preferred hydroxyl-removal, in fact not containing the functional group with linking agent (C) responding property.As described functional group, such as, the primary amine groups of bridging property or secondary amine, as the monomer containing described functional group, such as, (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid n-butylamino ethyl ester etc.
" in fact containing with the functional group of linking agent (C) responding property " refers to except completely not containing except described functional group, also comprise containing to hydroxyl and linking agent (C) and the situation of the described functional group of the admissible amount of degree that do not harm of reactivity.Specifically, in each polymkeric substance (A) and (B), described functional group is preferably less than 0.2 to the mol ratio of hydroxyl, and particularly preferably less than 0.1.
The polymerization methods of the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), for random co-polymer also can, block copolymer also can.
The weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is 500,000-300 ten thousand, preferably 700,000-250 ten thousand, particularly preferably 1,000,000-200 ten thousand.That is, the 1st (methyl) acrylic ester polymer (A) is high-molecular weight polymer composition.In addition, the weight average molecular weight in this specification sheets is the value of the polystyrene conversion that gel permeation chromatography (GPC) method measures.
As the 1st (methyl) acrylic ester polymer (A) weight average molecular weight as described in scope, polymkeric substance (A) just has larger molecular weight, and described structure X can be formed (supposition) well thus.
Weight average molecular weight as the 1st (methyl) acrylic ester polymer (A) be 500,000 have that gel fraction is low less than, the tackiness agent obtained, the possibility of weather resistance and reusability difference.In addition, when the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is more than 3,000,000, degenerate with the intermiscibility of the 2nd (methyl) acrylic ester polymer (B) etc., the possibility that the tackiness agent obtained has stress relaxation rate to be deteriorated.
On the other hand, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000-30 ten thousand, preferably 10,000-20 ten thousand, particularly preferably 50,000-10 ten thousand.That is, the 2nd (methyl) acrylic ester polymer (B) is low-molecular weight polymer composition.
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, has contribution to excellent stress relaxation rate.That is, the 2nd (methyl) acrylic ester polymer (B) weight average molecular weight as 8000 less than, good three-dimensional netted structure is just difficult to obtain.On the other hand, if the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is more than 300,000, with the 1st (methyl) acrylic ester polymer (A) etc. and intermiscibility be deteriorated, the insertion of the polymkeric substance (A) in the three-dimensional netted tectosome that polymkeric substance (B) is formed will be insufficient, its result, the weather resistance of the tackiness agent obtained and reusability have the occasion of variation.
In present embodiment, described the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic polymer (B), respectively can a kind be used alone, but also two or more combinationally uses.
To the 1st (methyl) acrylic ester polymer (A) 100 ratio of the 2nd (methyl) acrylic ester polymer (B) of mass parts, 5-50 mass parts is preferred, being particularly preferably with 5-40 mass parts, is preferred with 10-30 mass parts further.
From the tackiness agent that the tackiness composition containing the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) with described ratio obtains, described structure X can be formed (supposition) well.
As linking agent (C), can exemplify isocyanates linking agent, epoxies linking agent, aziridines linking agent and metal complex class linking agent etc., be wherein preferred with the isocyanates linking agent that the reactivity of the hydroxyl with polymkeric substance (A) and (B) is excellent.
Isocyanates linking agent, at least comprises polyisocyanate compounds.As polyisocyanate compounds, tolylene diisocyanate can be exemplified, diphenylmethanediisocyanate, the aromatic poly-isocyanate of p-Xylol group diisocyanate etc., the aliphatic polymeric isocyanate of hexamethylene diisocyanate etc., isophorone diisocyanate, the ester ring type polymeric polyisocyanate etc. of hydrogenation diphenylmethanediisocyanate etc., and their biuret body, chlorinated isocyanurates body, they and ethylene glycol can be exemplified further, propylene glycol, dimethyltrimethylene glycol, the affixture etc. of the compound containing low molecule active hydrogen of TriMethylolPropane(TMP) and castor-oil plant wet goods.
Described linking agent (C), can a kind be used alone, or two or more use that combines.
The amount of linking agent (C) is, the bridging property base of described linking agent (C) (such as, isocyanate group) amount to the hydroxyl of the 2nd (methyl) acrylic ester polymer (B), the amount of usual 0.05-5 equivalent, the amount of preferred 0.1-3.5 equivalent, the particularly amount of preferred 0.3-1.0 equivalent.The amount of described bridging property base be 0.05 equivalent less than occasion, the gel fraction of the tackiness agent obtained is low, has the possibility that can not give full play to cohesive force.In addition, the amount of described bridging property base is as more than 0.1 equivalent, and particularly more than 0.3 equivalent, the weather resistance of the tackiness agent obtained can be excellent further.On the other hand, as described in bridging property base amount 3.5 equivalent below, the clinging power of the tackiness agent obtained can be guaranteed fully.Further, below amount 1.0 equivalent of described bridging property base, linking agent (C) is formed with contribution only to the three-dimensional netted structure of polymkeric substance (B), effectively can prevent (supposition) the crosslinked of polymkeric substance (A).Its result, the stress relaxation rate of the tackiness agent obtained is excellent.
The tackiness composition of present embodiment, preferably, further containing silane coupling agent (D).As contained this silane coupling agent (D), the alkoxysilyl groups of silane coupling agent (D) etc. can act on the surface of the to-be-adhered object of glass substrate etc., the occasion of such as polarized light piece laminating on liquid-crystalline glasses unit etc., tackiness agent and liquid-crystalline glasses unit and between adherence can become better.
As this silane coupling agent (D), be the silicoorganic compound at least containing 1 alkoxysilyl group in molecule, have intermiscibility with tackiness agent composition, and have the thing of photopermeability, such as transparent in fact thing as well.The addition of such silane coupling agent (D), to the 1st (methyl) acrylic ester polymer (A) 100 mass parts be 0.01-0.5 mass parts be preferred, particularly 0.05-0.3 mass parts is preferred.
As the concrete example of silane coupling agent (D), can the polymerizability of exemplified by vinyl Trimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane etc. containing the silicon compound of unsaturated group; The silicon compound with epoxy structure of 3-glycidyl ether propyl trimethoxy silicane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.; 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane etc. containing aminosilicon compounds; 3-r-chloropropyl trimethoxyl silane; 3-isocyanic ester propyl-triethoxysilicane etc.These, get final product a kind and be used alone, but also two or more use that combines.
Described tackiness composition, as required, normally used various additive in acrylic acid or the like tackiness agent can be added on, such as charged preventor, adhesion imparting agent, antioxidant, UV light absorber, light stabilizer, tenderizer, filling agent and refractive index adjusters etc.
(manufacture method of tackiness composition)
Described tackiness composition, 1st (methyl) acrylic ester polymer (A) and, 2nd (methyl) acrylic ester polymer (B) manufactures respectively, while they being mixed, linking agent (C) and desired silane coupling agent (D) can be added in the arbitrary stage.
As preferred concrete example, be by (methyl) acrylic ester polymer (A) and (B), manufacture with common radical polymerization respectively.The polymerization of (methyl) acrylic ester polymer (A) and (B), as required, can use polymerization starter, carry out with solution polymerization process etc.As polymerization solvent, ethyl acetate, ro-butyl acetate, Sucrose Acetate base ester, toluene, acetone, hexane can be exemplified, methyl ethyl ketone etc., more than 2 kinds also with also can.
As polymerization starter, azo compound and organo-peroxide etc. can be exemplified, more than 2 kinds also with also passable.As azo compound, can 2 be exemplified, 2 '-azobisisobutylonitrile cyanogen, 2,2 '-azo two (2-methyl fourth cyanogen), 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-cyano group valeric acid), 2,2 '-azo two (2-hydroxymethyl third cyanogen) and 2,2 '-azo two [2-(2-miaow sits beautiful jade-2-base) propane] etc.
As organo-peroxide; benzoyl peroxide, benzoyl hydroperoxide t-butyl ester, isopropyl benzene hydroperoxide, diisopropyl peroxydicarbonate, di n propyl peroxy dicarbonate, two (2-ethoxyethyl group) peroxydicarbonate, peroxide new certain herbaceous plants with big flowers acid t-butyl ester, peroxide trimethylacetic acid t-butyl ester, (3 can be exemplified; 5,5-trimethyl acetyl base) superoxide, two propionyl superoxide and diacetyl superoxide etc.
In addition, in described Polymerization Engineering, moved the cooperation of agent by the chain of 2 mercapto ethanol etc., the weight average molecular weight of the polymkeric substance obtained can be adjusted.
Then, the solution of the polymkeric substance obtained (A) and (B) is mixed, adds dilution solvent.Afterwards, linking agent (C) and desired silane coupling agent (D) are added, and mix fully, just obtain the tackiness composition (coating solution) with solvent dilution.
Diluting solvent used during the coating solution obtained as diluting tackiness composition, can exemplify the aliphatic hydrocarbon of hexane, heptane and hexanaphthene etc.; The aromatic hydrocarbons of toluene and dimethylbenzene etc.; The halohydrocarbon of methylene dichloride and ethylene dichloride etc.; The alcohol of methyl alcohol, ethanol, propyl alcohol, butanols and 1-methoxyl group 2-propyl alcohol etc.; The ketone of acetone, methyl ethyl ketone, 2 pentanone, isophorone, pimelinketone etc.; Ethyl acetate, 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 the modulation so obtained, if in the scope that can be coated with just can, have no particular limits, can select aptly according to situation.Such as, the concentration of tackiness composition can be diluted for 10-40 quality %.In addition, when obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as tackiness composition has the possible viscosity etc. of coating, does not add diluting solvent passable yet.In this occasion, tackiness composition can seal fixedly becomes coating solution.
(tackiness agent)
The tackiness agent of present embodiment, for described tackiness composition is cross-linked and obtain.Being cross-linked of described tackiness composition, can carry out heat treated and carry out.In addition, this heat treated, can double as the drying treatment when the volatilization of the dilution solvent by tackiness composition etc.
Carrying out the occasion of heat treated, Heating temperature 50-150 DEG C is that preferably particularly 70-120 DEG C is preferred.In addition, heat-up time, within 30 seconds-3, be divided into preferably, particularly within 50 seconds-2, be divided into preferably.Further, after heat treated, carry out the maturation of 1-2 week degree at normal temperature (such as, 23 DEG C, 50%RH), for particularly preferably.
By described heat treated (and maturation), linking agent (DEG C) is while carrying out being cross-linked with the 2nd (methyl) acrylic ester polymer (B), have the 1st (methyl) acrylic ester polymer (A) to insert in its three-dimensional netted structure, described structure X-shaped becomes (supposition).
The tackiness agent of present embodiment, to the clinging power of non-alkali glass, 0.1-25N/25mm is preferably, is particularly preferred with 2-20N/25mm.In addition, in this said clinging power, carry out 180 ° of clinging powers (peeling rate 300mm/min) peeled off according to JISZ0237, at 0.5MPa, at 50 DEG C, carry out 20 points of pressurizations, after attaching with to-be-adhered object, at 23 DEG C, after carrying out under the condition of 50%RH placing for 24 hours, carry out measuring.As clinging power as described in scope in, where applicable on the optics of polarized light piece etc., float and stripping etc. just can be prevented from.
The tackiness agent of present embodiment, after attaching to described to-be-adhered object, further at 23 DEG C, under the condition of 50%RH, carry out the clinging power (attaching the clinging power after 14 days) after placing for 14th, be that preferably particularly 2-20N/25mm is preferred with 0.1-25N/25mm.So suppressed to the rising of clinging power in time, the tackiness agent of present embodiment, can be evaluated as reusability excellent.
Tackiness agent described above, as used for optical part be preferably use, such as, carry out bonding between the optics of polarized light piece (polarizing film) and polarizer (phase-contrast film) etc., or polarized light piece (polarizing film) and bonding between polarizer (phase-contrast film) and glass substrate just can use well.The adhering agent layer of the tackiness agent formation of present embodiment, stress relaxation rate is very excellent, the occasion that the dimensional change of to-be-adhered object is large, the stress occurred by its dimensional change is absorbed by adhering agent layer and relaxes, even if therefore life-time service is also difficult to peel off from to-be-adhered object, meanwhile, can effectively to be prevented for light leak during optics like that with described.That is, the tackiness agent of present embodiment, can reach resistance to light leakage and weather resistance and two sides all good.Further, the tackiness agent of present embodiment, has good reusability, in addition, owing to not having acids, to be made up of or occasion excellent corrosion resistance containing metal at to-be-adhered object metal.
(adhesive sheet)
As shown in Figure 1, the adhesive sheet 1A of the 1st embodiment, from lower, the adhering agent layer 11 being followed successively by stripping film 12 and being stacked in the release surface of stripping film 12, the base material 13 that adhering agent layer 11 is stacked is formed.
In addition, as shown in Figure 2, the adhesive sheet 1B of the 2nd embodiment, it is configured to have 2 pieces of stripping film 12a, 12b, and this stripping film 12a of 2 pieces, and the tackiness agent that 12b seizes on both sides by the arms becomes 11, and adhering agent layer 11 and this 2 release surface connect thus.In addition, the release surface of the so-called stripping film in this specification sheets, for having the face of separability in stripping film, even if no matter impose the face of lift-off processing or do not impose lift-off processing, but the face with separability is all included in this concept.
No matter in adhesive sheet 1A or 1B, adhering agent layer 11 is all that above-mentioned tackiness composition is cross-linked and the tackiness agent that obtains.
The thickness of adhering agent layer 11, is suitable for determining according to the application target of adhesive sheet 1A, 1B, usual 5-100 μm, the scope of preferred 10-60 μm, such as, as optics, particularly as the occasion of the adhering agent layer of polarized light piece, preferred 10-50 μm, particularly 10-30 μm is preferred.
As base material 13, particularly do not limit, the thing of the common substrate sheets use as adhesive sheet can use.Such as, outside optics, use woven or the non-woven fabrics of the fiber of artificial silk, acrylate copolymer and polyester etc.; The stationery of upper matter paper, glassine paper, impregnation paper and art paper etc.; The tinsel of aluminium and copper etc.; The foam of polyurethane foaming body and foam polyethylene etc.; The polyester film of polyethylene terephthalate, polybutylene terephthalate, PEN etc.; The cellulosefilm of polyurethane film, polyethylene film, polypropylene film and triacetyl cellulose etc.; Poly-ethylene dichloride base film; Poly-inclined chloroethylenes base film; Polyvinyl alcohol film; Ethylene vinyl acetate base co-polymer film; Polystyrene film; Polycarbonate film; Acrylic resin films; Norbornene type resin film; The plastics film of cyclenes resin film etc.; These stack of more than two kinds etc.Plastics film, an axial compression prolong also can or two axial compressions prolong and also can.
As optics, polarized light piece (polarizing film), polarisation can be exemplified, polarizer (phase-contrast film), angle of visibility mend reward film, briliancy improves film, contrast gradient improves film, liquid crystal polymer film, diffusion film and semi-penetration film etc.Wherein polarized light piece (polarizing film), be easy to shrink, dimensional change is large, from the viewpoint of resistance to light leakage, as the use object of the tackiness agent (described adhering agent layer 11) of present embodiment, is most suitable.
The thickness of base material 13, different according to its kind institute, the occasion of such as optics, is generally 10 μm-500 μm, preferably 50 μm-300 μm.
As stripping film 12, 12a, 12b, polyethylene film can be exemplified, polypropylene film, polybutene film, polybutadiene membrane, poly-methyl pentene film, poly-ethylene dichloride base film, ethylene dichloride base co-polymer film, pet film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate base film, amberlite membrane of lipoprotein, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylic ester copolymerization thing film, polystyrene film, polycarbonate film, Kapton and fluorine resin film etc.In addition, these crosslinked film also uses.Further, these overlay film also can use.
The release surface (particularly adhering agent layer 11 and the face connect) of described stripping film, preferably imposes lift-off processing.As the stripper used in lift-off processing, the stripper of alcohol acids, type siloxane, fluorine class, unsaturated polyester class, polyolefins and wax class can be exemplified.
The thickness of stripping film 12,12a, 12b has no particular limits, and is generally 20-150 μm of degree.
The manufacture of described adhesive sheet 1A, is be coated with by the solution (coating solution) containing described tackiness composition in the release surface of stripping film 12, carries out heat treated, after adhering agent layer 11 is formed, by stacked for base material 13 on this adhering agent layer 11.Afterwards, being set to preferably during maturation.
In addition, the condition of heat treated and maturation, as above-mentioned.
In addition, in order to carry out the manufacture of described adhesive sheet 1B, in the release surface of a stripping film 12a (or 12b), coating solution containing described tackiness composition is coated with, carry out heat treated, after adhering agent layer 11 is formed, coincide in this adhering agent layer 11 and the release surface of another stripping film 12b (or 12a).
The coating process of described coating solution, can exemplify that rod is coated with method, scrapes the skill in using a kitchen knife in cookery, rolling method, plate are coated with method, die coating methods and gravure coating method etc.
Such as, 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 described adhesive sheet 1A is peeled off, the adhering agent layer 11 and the liquid crystal cells that expose are fitted.
In addition, such as, between liquid crystal cells and polarized light piece polarizer configuration liquid crystal display device manufacture in, as an example, first, adhesive sheet 1B stripping film 12a (or 12b) is peeled off, the adhering agent layer 11 exposed of adhesive sheet 1B and polarizer are fitted.Then, will the stripping film 12 of the adhesive sheet 1A of polarized light piece be used to peel off as base material 13, the adhering agent layer 11 exposed of adhesive sheet 1A be fitted with 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, 1B, adhering agent layer 11 stress relaxation rate is very excellent, so be applicable to the bonding occasion of such as polarized light piece, the stress occurred due to the distortion of polarized light piece is absorbed mitigation (supposition) by adhering agent layer 11, thus, excellent resistance to light leakage and high weather resistance can be played.
Embodiment described above, records for ease of the understanding of the present invention, to the present invention without any restriction.Therefore, each key element disclosed in described embodiment comprises all design alterations and equivalent that belong to technical scope of the present invention.
Such as, the stripping film 12 of adhesive sheet 1A just can omit, and one of them of the stripping film 12a in adhesive sheet 1B, 12b also can be omitted.
[embodiment]
Below, according to embodiment etc., the present invention is specifically described further, but scope of the present invention is not limited to these embodiment etc.
(embodiment 1)
1. the modulation of polymkeric substance (A)
To in the reaction vessel with stirrer, thermometer, reflux cooler, dripping device and nitrogen ingress pipe, add n-butylacrylate 99.0 mass parts, vinylformic acid 2-hydroxyethyl ester 1.0 mass parts, ethyl acetate 200 mass parts, and 2,2 '-azobisisobutylonitrile cyanogen 0.08 mass parts, the air nitrogen replacement in described reaction vessel.Stir under this nitrogen atmosphere, reaction soln is warming up to 60 DEG C, after carrying out reaction in 16 hours, be cooled to room temperature.At this, carry out molecular weight determination by one of the solution obtained by following method, the generation of the polymkeric substance (A) of weight average molecular weight 1,570,000 is identified.
2. the modulation of polymkeric substance (B)
In the reaction vessel with stirrer, thermometer, reflux cooler, dripping device and nitrogen ingress pipe, by n-butylacrylate 85.0 mass parts, vinylformic acid 2-hydroxyethyl ester 15.0 mass parts, ethyl acetate 200 mass parts and 2,2 '-azobisisobutylonitrile cyanogen 0.08 mass parts adds, and the air nitrogen in described reaction vessel is replaced.This nitrogen atmosphere stirs below, while make reaction soln heat up 60 DEG C, carry out 16 hours anti-after, be cooled to room temperature.At this, carry out molecular weight determination by one of the solution obtained by following method, the generation of the polymkeric substance (B) of weight average molecular weight 60,000 is identified.
3. the modulation of tackiness composition
After polymkeric substance (B) 20 mass parts (solids component scaled value) obtained in polymkeric substance (A) 100 mass parts (solids component scaled value) obtained in described engineering (1) and described engineering (2) is mixed, as linking agent (C), Xylene Diisocyanate affixture (Mitsui Chemicals urethane Inc., trade(brand)name " TAKENATED-110N ") 3.0 mass parts being equivalent to the TriMethylolPropane(TMP) of the amount of hydroxyl 0.6 equivalent of polymkeric substance (B) is added.Finally, as silane coupling agent (D), 3-glycidyl ether propyl trimethoxy silicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ") 0.3 mass parts is added, stir fully, obtain the diluting soln of tackiness composition.
In addition, the ratio of the monomer of cooperation, the amount (H [OH]) of the hydroxyl in polymkeric substance (A) 100g is 8.62mmol, and the amount (L [OH]) of the hydroxyl in polymkeric substance (B) 20g is 25.84mmol.Therefore, to mole number of the hydroxyl in polymkeric substance (A) 100 mass parts, the mole number object ratio (L [OH]/H [OH]) of the hydroxyl in polymkeric substance (B) 20 mass parts is 3.00.
At this, table 1 is listed in the cooperation of described tackiness composition.In addition, shown in the details of the contracted notation etc. recorded in table 1 is following.
[polymkeric substance (A) and (B)]
BA: n-butylacrylate
AA: vinylformic acid
DM: methacrylic acid N, N-dimethyl aminoethyl ester
HEA: vinylformic acid 2-hydroxyethyl ester
H [OH] (mmol): using polymkeric substance (A) addition (mass parts) as (g)
Mole number of the hydroxyl calculated
L [OH] (mmol): using mole number of the hydroxyl that polymkeric substance (B) addition (mass parts) calculates as (g)
[isocyanates linking agent (C)]
XDI-TMP: the Xylene Diisocyanate affixture (Mitsui Chemicals urethane Inc., trade(brand)name " TAKENATED-110N ") of TriMethylolPropane(TMP)
TDI-TMP: the tolylene diisocyanate affixture (Japanese polyurethane Inc., trade(brand)name " CORONET-L ") of TriMethylolPropane(TMP)
[silane coupling agent (D)]
KBM403:3-glycidyl ether propyl trimethoxy silicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ")
By the diluting soln of tackiness composition obtained, stripping film (Lindeke Co., Ltd's system of lift-off processing has been carried out at a face type siloxane stripper of pet film, SP-PET3811, thickness: 38 μm) lift-off processing face carry out scraper for coating, its dried thickness is made to be 25 μm, carry out 1 minute heat treated at 90 DEG C, form adhering agent layer.
Then, by what be made up of the discoid polarizing film with liquid crystal layer, the polarized light piece that polarizing film and angle of visibility expand film integration is fitted, the surface of the exposing surface of adhering agent layer and disc-like liquid crystal layer is connected, at 23 DEG C, carry out maturation on the 7th under 50%RH, obtain the polarized light piece with adhering agent layer.
(embodiment 2-10, comparative example 1-7)
Except kind and the ratio of each monomer by forming tackiness composition, the kind of linking agent and silane coupling agent and use level, beyond the proportioning change as shown in table 1 of polymkeric substance (A) and polymkeric substance (B), carry out the manufacture with adhering agent layer polarized light piece similarly to Example 1.
At this, above-mentioned weight average molecular weight (Mw) is, carries out the weight average molecular weight of the polystyrene conversion measuring (GPC mensuration) with gel permeation chromatography (GPC) by following condition.
< condition determination >
GPC determinator: TOSOH Inc., HLC-8020
GPC post (following sequentially passes through): TOSOH Inc.
TSKguardcolumNHXL-H
TSKgelGMHXL(×2)
TSKgelG2000HXL
Measure solvent: tetrahydrofuran (THF)
Measure temperature: 40 DEG C
(experimental example 1) (light leak experiment)
By the polarized light piece with adhering agent layer obtained in embodiment or comparative example, be adjusted to 233mm × 309mm size with cutting device (the super cutter of Di Ye manufacturing company system, PN1-600).Stripping film is peeled off, after the adhering agent layer exposed is attached at non-alkali glass (Corning Incorporated's system, hawk XG), with 0.5MPa in the still that the former making of fruit is made, 50 DEG C, pressurizes 20 minutes.In addition, described laminating, it is Niccol cross state (polarizing axis: ∠ 45 °, ∠ 135 °) that the polarized light piece with adhering agent layer be made to become polarizing axis.In this condition, after carrying out under 80 DEG C of dry environment placing for 250 hours, 23 DEG C, carry out under the environment of 50%RH placing for 2 hours, made sample, carry out light leak evaluation by method shown below.The results are shown in table 2.
< light leak is evaluated: visual >
Described sample is arranged at flat head lamp (electric flux industry Inc., HF-SL-A312LC, illumination: 26,000Lux, briliancy: 10,000cd) on, (can Ni Ka Minolta Inc. with two-dimensional color brightness photometer, CA-2000) carry out a pinch shadow, carry out the conversion of briliancy distributed image with parsing software (can Ni Ka Minolta Inc., CA-S20w).The briliancy distributed image of the sample obtained, evaluates by the evaluation base Huaihe River shown in Fig. 3.
(experimental example 2) (durability evaluation)
By the polarized light piece with adhering agent layer obtained in embodiment or comparative example, be adjusted to 233mm × 309mm size with cutting device (the super cutter of Di Ye manufacturing company system, PN1-600).Stripping film is peeled off, after the adhering agent layer exposed is attached at non-alkali glass (Corning Incorporated's system, hawk XG), with the made still of the former making of chestnut at 0.5MPa, 50 DEG C, 20 points of pressurizations.
Afterwards, under dropping into the environment of following durable condition, observe with 10 times of magnifying glasses after 500 hours.Appearance change is observed with following base Huaihe River.The results are shown in table 2.
In ◎: 4 limits, no problem
In zero: 4 limit, the position no problem of more than 0.6mm from peripheral end
×: at least 1 limit on 4 limits, from peripheral end, the position of more than 0.6mm, observes and floats, and peels off, foaming, the abnormal appearance of the tackiness agent of more than the 0.1mm of striped etc.
The durable condition > of <
60 DEG C, relative humidity 90%RH
(experimental example 3) (reusability evaluation)
The polarized light piece with adhering agent layer obtained in embodiment or comparative example is carried out severing, makes 25mm wide, the sample that 100mm is long.From this sample, stripping film is peeled off, between the adhering agent layer exposed, sample is attached in non-alkali glass (Corning Incorporated's system, hawk XG), thereafter, with the automatic still of Guo Yuan manufacturing company at 0.5MPa, 50 DEG C, carry out 20 points of pressurizations.Then, carry out under 50 DEG C of dry conditions placing for 48 hours, 23 DEG C, under the condition of 50%RH, carry out damping in 3 hours.Afterwards, from non-alkali glass, sample hand is peeled off, visual valuation is carried out to the pollution on the surface of described non-alkali glass.Evaluate and carry out with following base Huaihe River.The results are shown in table 2.
Zero: paneless pollution tackiness agent remaining
△: only have the remaining of the pollution tackiness agent of few glass
×: the pollution tackiness agent of glass significantly remaining
(experimental example 4) (evaluation of erosion resistance)
The stripping film with the polarized light piece of adhering agent layer obtained in embodiment or comparative example is peeled off, after being fitted by Copper Foil (thickness: 80 μm), 60 DEG C, under the atmosphere of 90%RH, carries out keeping in 500 hours.Afterwards, from described Copper Foil, the polarized light piece with adhering agent layer is peeled off, visual observation is carried out to the surface of the Copper Foil exposed, the presence or absence of corrosion is confirmed.The results are shown in table 2.
Zero: corrosion-free
×: there is corrosion
(experimental example 5) (evaluation of mist degree (haze) value)
The tectosome that formed by the stripping film/adhering agent layer obtained in the manufacturing processed of embodiment or comparative example (thickness: 25 μm) (polarized light piece attach before tectosome) in addition Huaihe River is standby.Fitting with soda-lime glass (mist degree (haze) value 0%) in the adhering agent layer surface of being exposed by this tectosome, is peeled off by stripping film, make working sample.
By described working sample, by mist degree (haze) instrument (Japanese electricity Se industrial system, NDH2000), carry out mist degree (haze) value (%) (abbreviation is Hz (%)) by JISK7105 to measure.In addition, the scope of preferred mist degree (haze) value is 0-3%, within the scope of this, be expressed as zero, to be describedly extraneously expressed as ×.The results are shown in table 2.
[table 1]
Table 1 (continuous 1)
Table 1 (continuous 2)
[table 2]
Can clearly learn from table 2, what obtain in an embodiment has in the polarized light piece of adhering agent layer, and resistance to light leakage and weather resistance are all excellent, and reusability, erosion resistance and optical characteristics are also good simultaneously
Tackiness composition of the present invention and tackiness agent, optics can be applicable to well, such as can be applicable to the bonding of polarized light piece and polarizer well, in addition, adhesive sheet of the present invention, as the adhesive sheet used for optical part for polarized light piece and polarizer etc., can be suitable for well
[explanation of symbol]
1A, 1B... adhesive sheet
11... adhering agent layer
12,12a, 12b... stripping film
13... base material.
Claims (9)
1. a tackiness composition, is characterized in that:
Containing the 2nd (methyl) acrylic ester polymer (B) and linking agent (C) that weight average molecular weight be 500,000 ~ 3,000,000 the 1st (methyl) acrylic ester polymer (A), weight average molecular weight is 8000 ~ 300,000
Described 1st (methyl) acrylic ester polymer (A) and described 2nd (methyl) acrylic ester polymer (B), separately in fact not containing acidic groups, and as forming the monomer unit of described polymkeric substance, containing hydroxyl monomer
The hydroxyl monomer that described 1st (methyl) acrylic ester polymer (A) contains and the hydroxyl monomer that described 2nd (methyl) acrylic ester polymer (B) contains are one species,
Be 1.0 ~ 40 to the mol ratio of hydroxyl contained in described 2nd (methyl) acrylic ester polymer (B) of hydroxyl contained in described 1st (methyl) acrylic ester polymer (A);
Described 2nd (methyl) acrylic ester polymer (B), as the monomer unit forming this polymkeric substance, the described hydroxyl monomer containing 10 ~ 40 quality %.
2. tackiness composition according to claim 1, it is characterized in that: for described 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described 2nd (methyl) acrylic ester polymer (B) is 5 ~ 50 mass parts.
3. tackiness composition according to claim 1, it is characterized in that: described 1st (methyl) acrylic ester polymer (A) and described 2nd (methyl) acrylic ester polymer (B), except hydroxyl, in fact not containing having the functional group with described linking agent (C) responding property.
4. tackiness composition according to claim 1, is characterized in that: described linking agent (C) is isocyanates linking agent.
5. tackiness composition according to claim 4, it is characterized in that: the content of described isocyanates linking agent is, to the amount of the described hydroxyl contained in described 2nd (methyl) acrylic ester polymer (B), the isocyanate group of described isocyanates linking agent becomes the amount of 0.1 ~ 3.5 equivalent.
6. a tackiness agent, it forms for the tackiness composition described in any one of Claims 1 to 5 is crosslinked.
7. an adhesive sheet, has base material and adhering agent layer, it is characterized in that: described adhering agent layer is made up of tackiness agent according to claim 6.
8. adhesive sheet according to claim 7, is characterized in that: described base material is optics.
9. an adhesive sheet, the adhering agent layer having 2 pieces of stripping films and seized on both sides by the arms by described stripping film, described adhering agent layer connects with the release surface of described 2 pieces of stripping films thus, it is characterized in that, described adhering agent layer is made up of tackiness agent according to claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011143597A JP5611129B2 (en) | 2011-06-28 | 2011-06-28 | Adhesive composition, adhesive and adhesive sheet |
| JP2011-143597 | 2011-06-28 |
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| CN102888203A CN102888203A (en) | 2013-01-23 |
| CN102888203B true CN102888203B (en) | 2016-02-17 |
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| CN201210224025.0A Active CN102888203B (en) | 2011-06-28 | 2012-06-28 | Tackiness composition, tackiness agent and adhesive sheet |
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| JP (1) | JP5611129B2 (en) |
| KR (1) | KR101914457B1 (en) |
| CN (1) | CN102888203B (en) |
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| CN106133100A (en) * | 2014-03-28 | 2016-11-16 | 琳得科株式会社 | Cohesiveness compositions, sticker and adhesive sheet |
| JP6309404B2 (en) * | 2014-09-04 | 2018-04-11 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
| ES2960108T3 (en) | 2018-05-08 | 2024-02-29 | Sonja Tafelmeier | Automatic zipper closure system |
| JP7070981B2 (en) * | 2018-09-14 | 2022-05-18 | 日本カーバイド工業株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
| JP2024050319A (en) * | 2022-09-29 | 2024-04-10 | 日東電工株式会社 | Adhesive agent and adhesive sheet |
| JP2024050320A (en) * | 2022-09-29 | 2024-04-10 | 日東電工株式会社 | Adhesive agent and adhesive sheet |
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| CN1508184A (en) * | 2002-11-25 | 2004-06-30 | ס�ѻ�ѧ��ҵ��ʽ���� | Proenoic-acid resin composition, adhesive comprising same and optical laminated product containing said adhesive |
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| JP2000109771A (en) * | 1998-10-07 | 2000-04-18 | Lintec Corp | Adhesive sheet |
| 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 |
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- 2011-06-28 JP JP2011143597A patent/JP5611129B2/en active Active
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- 2012-05-17 TW TW101117517A patent/TWI534225B/en active
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| JPH10279907A (en) * | 1997-04-09 | 1998-10-20 | Soken Chem & Eng Co Ltd | Pressure sensitive adhesive composition for polarizing plate and polarizing plate |
| CN1508184A (en) * | 2002-11-25 | 2004-06-30 | ס�ѻ�ѧ��ҵ��ʽ���� | Proenoic-acid resin composition, adhesive comprising same and optical laminated product containing said adhesive |
| JP2004210866A (en) * | 2002-12-27 | 2004-07-29 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive resin composition, double-side pressure-sensitive adhesive tape using it, and touch panel using it |
| CN1918254A (en) * | 2004-04-23 | 2007-02-21 | Lg化学株式会社 | Acrylic pressure-sensitive adhesive composition for polarizing film |
| WO2009008470A1 (en) * | 2007-07-11 | 2009-01-15 | Soken Chemical & Engineering Co., Ltd. | Pressure-sensitive adhesive composition for polarizing plates and polarizing plate having pressure-sensitive adhesive layer |
| CN102356137A (en) * | 2009-03-16 | 2012-02-15 | 电气化学工业株式会社 | Pressure-sensitive adhesive and pressure-sensitive adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201307502A (en) | 2013-02-16 |
| TWI534225B (en) | 2016-05-21 |
| KR101914457B1 (en) | 2018-11-02 |
| JP2013010837A (en) | 2013-01-17 |
| JP5611129B2 (en) | 2014-10-22 |
| KR20130002265A (en) | 2013-01-07 |
| CN102888203A (en) | 2013-01-23 |
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