CN102888203A - Adhesive composition, adhesive and adhesive sheet - Google Patents
Adhesive composition, adhesive and adhesive sheet Download PDFInfo
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- CN102888203A CN102888203A CN2012102240250A CN201210224025A CN102888203A CN 102888203 A CN102888203 A CN 102888203A CN 2012102240250 A CN2012102240250 A CN 2012102240250A CN 201210224025 A CN201210224025 A CN 201210224025A CN 102888203 A CN102888203 A CN 102888203A
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- acrylic ester
- ester polymer
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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)
- Liquid Crystal (AREA)
- Polarising Elements (AREA)
Abstract
An adhesive composition, an adhesive and an adhesive sheet which are suitable for optical components, such as polarization light panel, etc., and have good stress relaxation rate, light leak resistance, good durability and good reusability are provided. The adhesive composition of the invention contains first (methyl) acrylic ester polymers (A) having a weight average molecular weight of 500-3000 thousands, second (methyl) acrylic ester polymers (B) having a weight average molecular weight of 80000-300 thousands and a cross-linking agent (C). The first (methyl) acrylic ester polymers (A) and the second (methyl) acrylic ester polymers (B) essentially do not contain acidic groups, and monomer units composing the polymers contain hydroxyl monomers. The hydroxyl monomers of the first (methyl) acrylic ester polymers (A) and the hydroxyl monomers of the second (methyl) acrylic ester polymers (B) are of the same kind. The molar ratio of the hydroxyl groups contained in the first (methyl) acrylic ester polymers (A) and the hydroxyl groups contained in the second (methyl) acrylic ester polymers (B) is 1.0-40.
Description
Technical field
The present invention relates to tackiness composition, tackiness agent (material that the tackiness composition is crosslinked) and adhesive sheet, particularly, relate to well suited tackiness composition, tackiness agent and the adhesive sheet of optics as polarized light piece etc.
Background technology
In general, in the liquid crystal panel, polarized light piece and polarizer are adhered to the glass substrate etc. of liquid crystal cells upper bonding in, the adhering agent layers that form from adhesion agent composition that use more.But, the optics of polarized light piece and polarizer etc. can be easy to by heat etc. shrink, its result, stacked adhering agent layer is difficult to its contraction is followed on described optics, (what is called is floated thereby peel off at the interface, peel off), departing from of optic axis of the optics of the stress cause the when contraction of optics can occur and produce light leak (so-called hickie).
As the method that it is prevented, it is high with clinging power to exemplify (1), and, the adhering agent layer that the form stability is good fits in the optics of polarized light piece etc., thereby the method that the contraction self that makes optics suppresses, or, the little adhering agent layer method of stress when (2) use the contraction of optics.As the method for (1), it is effective using the high adhering agent layer of such storage modulus of patent documentation 1 record.On the other hand, as the method for (2), it is effective that use can be carried out the soft corresponding good adhering agent layer of stress relaxation rate to the distortion of optics.
To using the method for (2), in patent documentation 2, put down in writing a kind of polarized light piece tackiness agent, it is for to be comprised by a kind of: (A) (methyl) alkyl acrylate and have co-polymer to the polymerizable monomer 0.5-20 % by weight of the functionality of linking agent, and its weight average molecular weight is high molecular (methyl) the acrylic acid or the like co-polymer 100 weight sections more than 1,000,000; (B) lower molecular weight (methyl) acrylic acid or the like (be total to) the polymkeric substance 20-200 weight section of weight average molecular weight below 30,000, the functional group that (C) can form crosslinked configuration has at least 2 multi-functional compounds 0.005-5 weight section to consist of in molecule.Functional group's partition ratio of [functional group of lower molecular weight (methyl) acrylic acid or the like (being total to) polymkeric substance]/[functional group of high molecular (methyl) acrylic acid or the like co-polymer] expression is in the scope of 0-15 % by weight.
Equally, enforcement to the method for described (2), at patent documentation 3, put down in writing a kind of optics adhesion agent composition, it is that (methyl) acrylic ester copolymerization thing (a) 100 mass parts of 800,000-2,000,000 and weight average molecular weight are that acrylic ester copolymerization thing mixture (A) and the linking agent (B) that (methyl) acrylic ester copolymerization thing (b) 20-100 mass parts below 50,000 forms consists of by weight average molecular weight, and described co-polymer (a) comprises the monomer unit that has with the reactive high functional group of linking agent (B), and described co-polymer (b) comprises the monomer unit with the reactivity of linking agent (B) functional group lower than the functional group of described co-polymer (a).
[patent documentation]
[patent documentation 1] JP 2006-235568 communique
No. 3533589 communique of [patent documentation 2] patent
[patent documentation 3] JP 2009-108122 communique
Patent documentation 2,3 disclosed tackiness agents, undertaken by (methyl) acrylic acid or the like co-polymer that makes high molecular preferentially crosslinked, thereby obtain the stress relaxation rate.But, the poor durability of described tackiness agent, for example under wet heat condition, peel off at the adhesion interface.The stress relaxation rate is not fully yet in addition, when it is used in the optics of polarized light piece etc., the occasion that light leak occurs is arranged.Further, attach tendency rear or in time clinging power rising, reusability is insufficient.
Summary of the invention
The present invention is in view of such actual state forms.Purpose of the present invention just provides that a kind of the stress relaxation rate is good when being applicable to the optics of polarized light piece etc., and when can prevent light leak, weather resistance is also good, further also good tackiness composition, tackiness agent and adhesive sheet of reusability.
Reach in order to make described purpose, the 1st, the invention provides a kind of tackiness composition, comprise that weight average molecular weight is 500,000-3,000,000 the 1st (methyl) acrylic ester polymer (A), 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 the 1st (methyl) acrylic ester polymer (A) and described the 2nd (methyl) acrylic ester polymer (B), respectively, do not contain in fact acidic groups, and the formation monomer unit as described polymkeric substance contains the hydroxyl monomer, the hydroxyl monomer that described the 1st (methyl) acrylic ester polymer (A) contains, the hydroxyl monomer that contains with described the 2nd (methyl) acrylic ester polymer (B) is one species, the hydroxyl that described the 1st (methyl) acrylic ester polymer (A) is contained, the mol ratio of the hydroxyl that described the 2nd (methyl) acrylic ester polymer (B) contains is 1.0-40 (invention 1).
Carry out the tackiness composition of described invention (invention 1) crosslinked and tackiness agent that obtain can be brought into play suitable cohesive force and good stress relaxation rate.Tackiness agent with this good stress relaxation rate, when being applicable to the optics of polarized light piece etc., two sides that can obtain anti-light leak and weather resistance are good, further also good adhesive sheet of reusability.In addition, each polymkeric substance of described tackiness composition, owing to substantially do not contain acidic groups, to-be-adhered object is the occasion of metal formation or the occasion that contains metal, described corrosion of metal can be suppressed.
In the described invention (invention 1), described the 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).
In the described invention (invention 1,2), to described the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described the 2nd (methyl) acrylic ester polymer (B) is preferably 5-50 mass parts (invention 3).
In the described invention (invention 1-3), described the 1st (methyl) acrylic ester polymer (A) and described the 2nd (methyl) acrylic ester polymer (B), beyond the preferred hydroxyl-removal, do not contain in fact with described linking agent (C) and have reactive functional group (invention 4).
In the described invention (invention 1-4), described linking agent (C) is preferably isocyanates linking agent (invention 5).
In the described invention (invention 5), the amount of described isocyanates linking agent, the amount of the described hydroxyl that described the 2nd (methyl) acrylic ester polymer (B) is contained for the isocyanate group of described isocyanates linking agent is the amount (invention 6) of 0.1-3.5 equivalent.
The 2nd, the present invention provides a kind of by described tackiness composition (invention 1-6) the crosslinked tackiness agent that forms (invention 7).
The 3rd, the present invention for having the adhesive sheet of base material and adhering agent layer, is characterized in that: described adhering agent layer consists of (invention 8) by described tackiness agent (invention 7).
In the described invention (invention 8), described base material, preferred light member (invention 9).
The 4th, the invention provides a kind of adhesive sheet, it is made of 2 pieces of stripping films and the adhesive layer of being seized on both sides by the arms by described 2 pieces stripping film, the release surface of adhering agent layer and 2 pieces of stripping films is joined thus, it is characterized in that: described adhering agent layer consists of (invention 10) by described tackiness agent (invention 7).
[effect of invention]
In the crosslinked tackiness agent that forms of tackiness composition of the present invention, make the low-molecular-weight polymkeric substance that in the past used as plasticizer carry out preferentially crosslinked, the three-dimensional netted structure of described low-molecular-weight polymer formation chemically crosslinked, in this three-dimensional netted structure, there is the polymkeric substance of a plurality of high molecular to insert, the polymer of high molecular is in bond, forms thus the crosslinked configuration (supposition) like intending between the polymer of high molecular.Thus, the tackiness agent that obtains can be brought into play suitable cohesive force and good stress relaxation rate, and when being applicable to the optics of polarized light piece etc., when light leak was prevented effectively, weather resistance was also good, and further reusability is also good.In addition, each polymkeric substance of tackiness composition of the present invention does not contain in fact acidic groups, so the occasion that to-be-adhered object is made of metal or the occasion that contains metal can suppress described metallic corrosion.
Description of drawings
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.
(visual) that Fig. 3 has a light leak experiment in the polarized light piece of adhering agent layer for expression estimated the figure in basic Huaihe River.
Has embodiment
Below, embodiments of the present invention are described.
(tackiness composition)
The tackiness composition of present embodiment, contain weight average molecular weight (Mw) and be the 2nd (methyl) acrylic ester polymer (B) and the linking agent (C) of 500,000-3,000,000 the 1st (methyl) acrylic ester polymer (A), weight average molecular weight (Mw) and 8000-30 ten thousand, preferably further contain silane coupling agent (D).In addition, in this manual, (methyl) acrylate has two sides' of acrylate and methacrylic ester the meaning.Other similar term too.In addition, the concept that also contains " co-polymer " in " polymkeric substance ".
The 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), respectively, do not contain in fact acidic groups, and described polymkeric substance contains hydroxyl monomer (molecule contains the monomer of hydroxyl) as the monomer unit that consists of, preferably, the carbon number of alkyl is (methyl) alkyl acrylate, hydroxyl monomer of 1-20 and not containing of using as required and the functional group's of responding property of linking agent (C) other the co-polymer of monomer.
As acidic groups, mainly exemplify carboxyl, other can exemplify sulfonic group and phosphate etc.The 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) do not contain in fact acidic groups, to-be-adhered object be the occasion that consists of of metal (for example, to-be-adhered object is the occasion of the electrode that consists of of tin indium oxide (ITO)) or the occasion that contains metal is (for example, to-be-adhered object contains the occasion of wire netting), described metallic corrosion can be inhibited.
At this, so-called " not containing in fact acidic groups ", refer to not contain outside the acidic groups fully, thereby also comprise the small permissible degree of the degree of corrosion of metal.Specifically, be as polymkeric substance (A) or component unit (B), contain the amount of acidic groups monomer, be generally 1 quality % less than, preferred 0.5 quality % less than, particularly preferred 0.1 quality % less than.
Carbon number as alkyl is (methyl) alkyl acrylate of 1-20, can exemplify (methyl) methyl acrylate, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid propyl diester, (methyl) n-butylacrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid n-hexyl ester, (methyl) vinylformic acid cyclohexyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) isooctyl acrylate ester, the positive certain herbaceous plants with big flowers base of (methyl) vinylformic acid ester, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid myristyl ester, (methyl) aliphatic acrylate and (methyl) stearyl acrylate base ester etc.They can be suitable for separately, also can be used in combination more than 2 kinds.
As the hydroxyl monomer, can exemplify (methyl) vinylformic acid hydroxyalkyl acrylate 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. etc.They can be suitable for separately, also can be used in combination more than 2 kinds.
In the tackiness composition of present embodiment, the hydroxyl monomer that hydroxyl monomer and the 2nd (methyl) acrylic ester polymer (B) that the 1st (methyl) acrylic ester polymer (A) contains contains is one species, and, 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) is contained contains is 1.0-40, preferred 3-30, particularly preferably 5-20.
In addition, in other words described mol ratio, refers to the mole number to the hydroxyl of the polymkeric substance in the tackiness composition (A) origin, the mole number purpose ratio of the hydroxyl of polymkeric substance (B) origin.For example, in the tackiness composition, when polymkeric substance (A) 100 mass parts and polymkeric substance (B) 20 mass parts cooperate, represent the mole number purpose ratio of the hydroxyl of described use level.In addition, " one species " in this specification sheets not only refers to same hydroxyl monomer, and the occasion that exists in same polymkeric substance also refers to the hydroxyl monomer same with the reactive essence of linking agent (C).
As described, hydroxyl for the hydroxyl monomer origin of same, the 2nd (methyl) acrylic ester polymer (B) is compared with the 1st (methyl) acrylic ester polymer (A), contain when amount is above together, when described tackiness composition is crosslinked, the 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, be more than the 1st (methyl) acrylic ester polymer (A) (high-molecular weight polymer) 2 molecules, do not follow direct chemical bond or only have few chemical bond to follow and insert, polymer (A) is in state that degree of freedom is to a certain degree arranged and in bond, thereby forms the crosslinked configuration (suppositions) (being also referred to as " constructing X " below the structure of so inferring) like intending.The 1st (methyl) acrylic ester polymer (A), the amount of hydroxyl is less, inserts well so be taken into account in the described three-dimensional netted structure.Have the tackiness agent of described structure X, can bring into play suitable cohesive force and good stress relaxation rate.Tackiness agent with so good stress relaxation rate when being applicable to the optics of polarized light piece etc., also can prevent float and peeling off etc. under the condition such as when anti-light leak was good, weather resistance was also good, and is damp and hot.In addition, even the 2nd (methyl) acrylic ester polymer (B) and the 1st (methyl) acrylic ester polymer (A) contain the occasion with the hydroxyl of amount, compare with the polymkeric substance (A) of high molecular, the density of the hydroxyl of low-molecular-weight polymkeric substance (B) is high, that cause owing to structure also can become seldom with the difficulty that contacts linking agent (C), polymkeric substance (B) preferentially reacts with linking agent (C) thus.Further, among the described structure X, owing to be not used for giving the uncrosslinked low molecular weight compositions of stress relaxation rate etc., so becoming just the oozing out etc. of low molecular weight compositions of problem in the tackiness agent of stress relaxation rate type in the past can not occur, its result, from the tackiness agent that the tackiness composition of present embodiment obtains, reusability is also good.
The 2nd (methyl) acrylic ester polymer (B), as consisting of monomer unit, preferably containing the hydroxyl monomer is 10-40 quality %, particularly contains 10-30 quality % for preferred, further 12-20 quality % contains promising preferred.The words that the hydroxyl monomer is contained in this scope, 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 the amount 10 quality % of hydroxyl monomer less than the time, the 2nd (methyl) acrylic ester polymer (B) crosslinked insufficient, the solidifying minute rate of handing over is low, and the possibility of weather resistance variation is arranged.On the other hand, surpass 40 quality % such as the amount of hydroxyl monomer, the 2nd (methyl) acrylic ester polymer (B) crosslinked excessively, the stress relaxation rate just has the possibility of variation, and after crosslinked, hydroxyl is remaining, particularly the weather resistance variation under wet heat condition.In addition, the upper limit of the amount of hydroxyl monomer is as fixing on 30 quality %, and the anti-light leak of the adhesive sheet that obtains will be further good.
In addition, the preferred amount of the hydroxyl monomer in the 1st (methyl) acrylic ester polymer (A), mol ratio by the amount of the hydroxyl monomer in described the 2nd (methyl) acrylic ester polymer (B) and above-mentioned hydroxyl is determined automatically.
As described other monomer, can exemplify (methyl) acrylate with aliphatics ring of (methyl) vinylformic acid cyclohexyl ester etc.; (methyl) acrylate that aromatic ring is arranged with (methyl) vinylformic acid phenyl 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, vinyl-acetic ester and the vinylbenzene etc. with tertiary amine groups of the non-crosslinked of N-dimethylaminopropyl ester etc.They can be suitable for separately, also can be used in combination more than 2 kinds.
Described other monomer among, (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., (methyl) vinylformic acid N particularly, N-dimethyl aminoethyl ester, there is the reaction of the hydroxyl that promotes in the polymkeric substance and linking agent (C) that the effect of catalyst of promotion is arranged, so in the 2nd (methyl) acrylic ester polymer (B), monomer unit as the formation of described polymkeric substance also can contain.
This occasion, the amount of (methyl) acrylate with tertiary amine groups of the described non-crosslinked in the 2nd (methyl) acrylic ester polymer (B), take 0.1-10 quality % as preferred, particularly 1-5 quality % is preferred.
At this, for described structure X is formed really, the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) beyond the preferred hydroxyl-removal, do not contain in fact the functional group with responding property of linking agent (C).As described functional group, for example, the primary amine groups of bridging property or secondary amine, as the monomer that contains described functional group, for example, (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid normal-butyl amino-ethyl ester etc.
" do not contain in fact the functional group with responding property of linking agent (C) " and refer to except do not contain fully the described functional group, comprise yet contain to hydroxyl and linking agent (C) and reactivity do not have described functional group's the situation of the admissible amount of the degree that harms.Specifically, each polymkeric substance (A) and (B) in, described functional group's the mol ratio to hydroxyl is preferably below 0.2, and is particularly preferred below 0.1.
The polymerization methods of the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B), for co-polymer at random also can, block copolymer also can.
The weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) is 500,000-3,000,000, and is preferred 700,000-2,500,000, particularly preferred 1,000,000-2,000,000.That is, the 1st (methyl) acrylic ester polymer (A) is the high-molecular weight polymer composition.In addition, the weight average molecular weight in this specification sheets, the value of the polystyrene conversion of measuring for gel permeation chromatography (GPC) method.
As the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) as described in the scope, polymkeric substance (A) just has larger molecular weight, described structure X can form (supposition) well thus.
As the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) be 500,000 less than, the tackiness agent that obtains have that gel fraction is low, weather resistance and the poor possibility of reusability.In addition, the weight average molecular weight of the 1st (methyl) acrylic ester polymer (A) was above 3,000,000 o'clock, degenerate with the intermiscibility of the 2nd (methyl) acrylic ester polymer (B) etc., the tackiness agent that obtains has the possibility of stress relaxation rate variation.
On the other hand, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) is 8000-30 ten thousand, and is preferred 10,000-200,000, particularly preferred 50,000-100,000.That is, the 2nd (methyl) acrylic ester polymer (B) is the low-molecular weight polymer composition.
As the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) as described in the scope, distinctive three-dimensional netted formation of structure in the tackiness composition of present embodiment has contribution to good stress relaxation rate.That is, the weight average molecular weight of the 2nd (methyl) acrylic ester polymer (B) as be 8000 less than, good three-dimensional netted structure just is difficult to obtain.On the other hand, weight average molecular weight such as the 2nd (methyl) acrylic ester polymer (B) surpasses 300,000, with the 1st (methyl) acrylic ester polymer (A) etc. and the intermiscibility variation, the insertion of the polymkeric substance (A) in the three-dimensional netted tectosome that forms to polymkeric substance (B) will be insufficient, its result, the weather resistance of the tackiness agent that obtains and reusability have the occasion of variation.
In the present embodiment, described the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic polymer (B) respectively can a kind use separately, also can be used in combination more than 2 kinds.
Ratio to the 2nd (methyl) acrylic ester polymer (B) of the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the 5-50 mass parts is preferred, particularly take the 5-40 mass parts as preferred, further take the 10-30 mass parts as preferred.
From the tackiness agent that the tackiness composition that contains the 1st (methyl) acrylic ester polymer (A) and the 2nd (methyl) acrylic ester polymer (B) with described ratio obtains, described structure X can form (supposition) well.
As linking agent (C), can exemplify isocyanates linking agent, epoxies linking agent, aziridines linking agent and metal complex class linking agent etc., wherein take with the reactive good isocyanates linking agent of polymkeric substance (A) and hydroxyl (B) as preferred.
The isocyanates linking agent comprises polyisocyanate compounds at least.As polyisocyanate compounds, can exemplify tolylene diisocyanate, 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 of hydrogenation diphenylmethanediisocyanate etc. etc., and their biuret body, the chlorinated isocyanurates body further can exemplify they and ethylene glycol, propylene glycol, dimethyltrimethylene glycol, the affixture of the compound that contains low molecular activity hydrogen of TriMethylolPropane(TMP) and castor-oil plant wet goods etc.
Described linking agent (C) can a kind uses separately, and use perhaps combines more than 2 kinds.
The amount of linking agent (C) is, the bridging property base of described linking agent (C) (for example, isocyanate group) to the amount of the hydroxyl of the 2nd (methyl) acrylic ester polymer (B), the amount of common 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 that obtains is low, and the possibility that can not give full play to cohesive force is arranged.In addition, the amount of described bridging property base is as being more than 0.1 equivalent, and particularly more than 0.3 equivalent, the weather resistance of the tackiness agent that obtains can be further good.On the other hand, below amount 3.5 equivalents of bridging property base, the clinging power of the tackiness agent that obtains can be guaranteed fully as described.Further, below amount 1.0 equivalents of described bridging property base, linking agent (C) is only to the contribution that is formed with of the three-dimensional netted structure of polymkeric substance (B), can effectively prevent (supposition) to polymkeric substance (A) crosslinked.Its result, the stress relaxation rate of the tackiness agent that obtains is good.
The tackiness composition of present embodiment, preferred, further contain silane coupling agent (D).As contain this silane coupling agent (D), the meetings such as alkoxysilyl group of silane coupling agent (D) act on the surface of the to-be-adhered object of glass substrate etc., such as the occasion that polarized light piece is fitted in the liquid-crystalline glasses unit etc., tackiness agent and liquid-crystalline glasses unit and between adherence can become better.
As this silane coupling agent (D), for containing at least the silicoorganic compound of 1 alkoxysilyl group in the molecule, with the tackiness agent composition intermiscibility is arranged, and have the thing of photopermeability, for example transparent in fact thing is for well.The addition of such silane coupling agent (D) is that the 0.01-0.5 mass parts is preferred to the 1st (methyl) acrylic ester polymer (A) 100 mass parts, and particularly the 0.05-0.3 mass parts is preferred.
As the concrete example of silane coupling agent (D), can the exemplified by vinyl Trimethoxy silane, the polymerizability of vinyltriethoxysilane, methacryloxypropyl trimethoxy silane etc. contains 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-aminopropyl methyl dimethoxysilane etc. contain amino silicon compound; The 3-r-chloropropyl trimethoxyl silane; 3-isocyanic ester propyl-triethoxysilicane etc.These get final product a kind and use separately, and use also can combine more than 2 kinds.
Described tackiness composition, as required, can be added on normally used various additives in the acrylic acid or the like tackiness agent, such as charged preventor, adhesion imparting agent, antioxidant, UV light absorber, light stabilizer, tenderizer, filling agent and specific refractory power adjusting agent etc.
(manufacture method of tackiness composition)
Described tackiness composition, the 1st (methyl) acrylic ester polymer (A) and, the 2nd (methyl) acrylic ester polymer (B) is made respectively, when their are mixed, can be in that the stage be added linking agent (C) and desirable silane coupling agent (D) arbitrarily.
As preferred concrete example, be with (methyl) acrylic ester polymer (A) and (B), use respectively common radical polymerization manufacturing.(methyl) acrylic ester polymer (A) and polymerization (B) as required, can be used polymerization starter, carry out with solution polymerization process etc.As the polymerization solvent, can exemplify ethyl acetate, ro-butyl acetate, acetic acid isobutyl, toluene, acetone, hexane, methyl ethyl ketone etc., 2 kinds are above also with also can.
As polymerization starter, can exemplify azo compound and organo-peroxide etc., 2 kinds are above also with also can.As azo compound, can exemplify 2,2 '-the two isobutyl cyanogen, 2 of azo, 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 esters), 4,4 '-azo two (4-cyano group valeric acid), 2,2 '-azo two (2-hydroxymethyl the third cyanogen) and 2,2 '-azo two [2-(the 2-miaow is sat beautiful jade-2-yl) propane] etc.
As organo-peroxide; can exemplify benzoyl peroxide, benzoyl hydroperoxide t-butyl ester, isopropyl benzene hydroperoxide, diisopropyl peroxydicarbonate, di n propyl peroxy dicarbonate, two (2-ethoxyethyl group) peroxide two carbonic ethers, the new certain herbaceous plants with big flowers acid of peroxide t-butyl ester, peroxide trimethylacetic acid t-butyl ester, (3; 5,5-trimethyl acetyl base) superoxide, two propionyl superoxide and diacetyl superoxide etc.
In addition, in the described Polymerization Engineering, move the cooperation of agent by the chain of 2 mercapto ethanol etc., the weight average molecular weight of the polymkeric substance that obtains can be adjusted.
Then, polymkeric substance (A) and the solution (B) that obtains is mixed, add the dilution solvent.Afterwards, linking agent (C) and desirable silane coupling agent (D) are added, and mix fully, just obtain the tackiness composition (coating solution) with the solvent dilution.
Used diluting solvent during the coating solution that obtains as the tackiness composition is diluted 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 kind solvent of ethyl cellosolve etc. etc.
The concentration viscosity of the coating solution of the modulation that so obtains, if in the scope that can be coated with just can, have no particular limits, can select aptly according to situation.For example, the concentration of tackiness composition can be diluted and is 10-40 quality %.In addition, when obtaining coating solution, the interpolation of diluting solvent etc. is not prerequisite, as long as the tackiness composition has the possible viscosity of coating etc., it is also passable not add diluting solvent.In this occasion, the tackiness composition can seal fixedly becomes coating solution.
(tackiness agent)
The tackiness agent of present embodiment obtains for described tackiness composition is crosslinked.Described tackiness composition crosslinked can carry out heat treated and carry out.In addition, this heat treated can double as the drying treatment with the volatilization of dilution solvent of tackiness composition etc. the time.
In the occasion of carrying out heat treated, Heating temperature 50-150 ℃ is preferred, and particularly 70-120 ℃ is preferred.In addition, be divided into preferably in 30 seconds-3 heat-up time, particularly be divided into preferred in 50 seconds-2.Further, after the heat treated, carry out the maturation of 1-2 week degree at normal temperature (for example, 23 ℃, 50%R H), for particularly preferably.
By described heat treated (and maturation), linking agent (℃) with the 2nd (methyl) acrylic ester polymer (B) carry out crosslinked in, 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 preferred, particularly take 2-20N/25mm as preferred.In addition, in this said clinging power, to carry out 180 ° of clinging powers of peeling off (peeling rate 300mm/min) according to JIS Z0237, at 0.5MPa, under 50 ℃, carry out pressurization in 20 minutes, with to-be-adhered object attach after, at 23 ℃, after carrying out under the condition of 50%RH placing in 24 hours, measure.Such as clinging power in described scope, where applicable on the optics of polarized light piece etc., float and peeling off etc. just can be prevented from.
The tackiness agent of present embodiment, after attaching to described to-be-adhered object, further at 23 ℃, the clinging power (attaching the clinging power after 14 days) after carrying out under the condition of 50%RH placing in 14th, take 0.1-25N/25mm as preferred, particularly 2-20N/25mm is preferred.So suppressed to the rising of in time clinging power, the tackiness agent of present embodiment, it is good to be evaluated as reusability.
Tackiness agent described above, be preferred the use as used for optical part, for example, carry out bondingly between the optics of polarized light piece (polarizing film) and polarizer (phase-contrast film) etc., or bonding between polarized light piece (polarizing film) and polarizer (phase-contrast film) and the glass substrate just can be used well.The adhering agent layer that the tackiness agent of present embodiment forms, the stress relaxation rate is very good, the occasion that the dimensional change of to-be-adhered object is large, the stress that is occured by its dimensional change is absorbed mitigation by adhering agent layer, even therefore life-time service also is difficult to peel off from to-be-adhered object, simultaneously, with described when like that being used for optics light leak can effectively be prevented.That is, the tackiness agent of present embodiment, it is all good to reach anti-light leak and weather resistance and two sides.Further, the tackiness agent of present embodiment has good reusability, in addition, owing to there is not acids, is made of or contains the occasion excellent corrosion resistance of metal metal at to-be-adhered object.
(adhesive sheet)
As shown in Figure 1, the adhesive sheet 1A of the 1st embodiment, under, the adhering agent layer 11 that is followed successively by stripping film 12 and is stacked in the release surface of stripping film 12, the base material 13 that is stacked at adhering agent layer 11 consists of.
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, the tackiness agent that 12b seizes on both sides by the arms becomes 11, and adhering agent layer 11 joins with these 2 release surface thus.In addition, the release surface of the so-called stripping film in this specification sheets, for having the face of separability in the stripping film, even no matter impose the face of lift-off processing or do not impose lift-off processing, but the face with separability all is included in this concept.
No matter in adhesive sheet 1A or 1B, adhering agent layer 11 all is the crosslinked and tackiness agent that obtains of above-mentioned tackiness composition.
The thickness of adhering agent layer 11, according to adhesive sheet 1A, the application target of 1B suits to determine, usually 5-100 μ m, the scope of preferred 10-60 μ m, for example, as optics, the occasion of the adhering agent layer of particularly using as polarized light piece, preferred 10-50 μ m, particularly 10-30 μ m are preferred.
As base material 13, particularly restriction, the thing of common substrate sheets use as adhesive sheet can use.For example, outside the 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 to one side chloroethylenes base film; The polyvinyl alcohol film; Ethene vinyl acetate base co-polymer film; Polystyrene film; Polycarbonate film; The acrylic resin film; The norbornene type resin film; The plastics film of cyclenes resin film etc.; These the stack more than 2 kinds etc.Plastics film, an axial compression prolong also can or two axial compressions prolong and also can.
As optics, can exemplify polarized light piece (polarizing film), polarisation, polarizer (phase-contrast film), angle of visibility benefit reward film, briliancy raising film, contrast gradient raising film, liquid crystal polymer film, diffusion film and semi-penetration film etc.Polarized light piece (polarizing film) wherein is easy to shrink, and dimensional change is large, from the viewpoint of anti-light leak, as the use object of the tackiness agent (described adhering agent layer 11) of present embodiment, is only.
The thickness of base material 13, different according to its kind institute, for example the occasion of optics is generally 10 μ m-500 μ m, preferred 50 μ m-300 μ m.
As stripping film 12,12a, 12b can exemplify polyethylene film, polypropylene film, the polybutene film, the polyhutadiene film, poly-methyl pentene film, poly-ethylene dichloride base film, ethylene dichloride base co-polymer film, pet film, polyethylene naphthalate film, the polybutylene terephthalate film, polyurethane film, ethene vinyl acetate base film, the 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 of described stripping film (particularly adhering agent layer 11 and the face that connects) preferably imposes lift-off processing.As the stripper that uses in the lift-off processing, can exemplify the stripper of alcohol acids, type siloxane, fluorine class, unsaturated polyester class, polyolefins and wax class.
Stripping film 12,12a, the thickness of 12b has no particular limits, and is generally 20-150 μ m degree.
The manufacturing of described adhesive sheet 1A is that the solution (coating solution) that will contain described tackiness composition on the release surface of stripping film 12 is coated with, and carries out heat treated, and is after adhering agent layer 11 formation, on this adhering agent layer 11 that base material 13 is stacked.Afterwards, being set to preferably during the maturation.
In addition, the condition of heat treated and maturation is as above-mentioned.
In addition, in order to carry out the manufacturing of described adhesive sheet 1B, on the release surface of a stripping film 12a (perhaps 12b), the coating solution that will contain described tackiness composition is coated with, carry out heat treated, after adhering agent layer 11 forms, coincide on the release surface with this adhering agent layer 11 and another stripping film 12b (perhaps 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 be coated with method, die coating method and notch board coating method etc.
For example, in the manufacturing of the liquid crystal display device that is made 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, adhering agent layer 11 and the liquid crystal cells that will expose are fitted.
In addition, for example, in the manufacturing of the liquid crystal display device that polarizer disposes between liquid crystal cells and polarized light piece, as an example, at first, the stripping film 12a (perhaps 12b) of adhesive sheet 1B is peeled off, the adhering agent layer that exposes 11 and the polarizer of adhesive sheet 1B are fitted.Then, will use the stripping film 12 of the adhesive sheet 1A of polarized light piece to peel off as base material 13, the adhering agent layer that exposes 11 and the described polarizer of adhesive sheet 1A be fitted.Further, from the adhering agent layer 11 of described adhesive sheet B another stripping film 12b (perhaps 12a) is peeled off, the adhering agent layer that exposes 11 and the liquid crystal cells of adhesive sheet B are fitted.
Above adhesive sheet 1A, 1B, adhering agent layer 11 stress relaxation rates are very good, so be applicable to for example bonding occasion of polarized light piece, the stress that occurs owing to the distortion of polarized light piece is absorbed by adhering agent layer 11 and relaxes (supposition), thus, can bring into play good anti-light leak and high weather resistance.
Embodiment described above is put down in writing in order to be easy to the understanding of the present invention, to the present invention without any restriction.Therefore, disclosed each key element of described embodiment comprises all design alterations and the equivalent that belongs to technical scope of the present invention.
For example, the stripping film 12 of adhesive sheet 1A just can omit, the stripping film 12a among the adhesive sheet 1B, and one of them of 12b also can be omitted.
[embodiment]
Below, according to embodiment etc. the present invention is further specifically described, but scope of the present invention is not limited to these embodiment etc.
(embodiment 1)
1. the modulation of polymkeric substance (A)
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 '-two isobutyl cyanogen 0.08 mass parts of azo, the air nitrogen replacement in the described reaction vessel.Stir under this nitrogen atmosphere, reaction soln is warming up to 60 ℃, after carrying out reacting in 16 hours, be cooled to room temperature.At this, an one of the solution that obtains is carried out molecular weight determination with following method, the generation of the polymkeric substance of weight average molecular weight 1,570,000 (A) is identified.
2. the modulation of polymkeric substance (B)
In the reaction vessel with stirrer, thermometer, reflux cooler, dripping device and nitrogen ingress pipe, with n-butylacrylate 85.0 mass parts, vinylformic acid 2-hydroxyethyl ester 15.0 mass parts, ethyl acetate 200 mass parts and 2,2 '-the two isobutyl cyanogen 0.08 mass parts addings of azo, the air in the described reaction vessel is replaced with nitrogen.This nitrogen atmosphere bottom stirs, and the limit makes reaction soln heat up 60 ℃, carry out 16 hours anti-after, be cooled to room temperature.At this, an one of the solution that obtains is carried out molecular weight determination with following method, the generation of the polymkeric substance of weight average molecular weight 60,000 (B) is identified.
3. the modulation of tackiness composition
With polymkeric substance (B) 20 mass parts (solids component scaled value) that obtain in polymkeric substance (A) 100 mass parts (solids component scaled value) that obtain in the described engineering (1) and the described engineering (2) mix after, as linking agent (C), Xylene Diisocyanate affixture (Mitsui Chemicals urethane company system, trade(brand)name " TAKENATED-110N ") 3.0 mass parts of TriMethylolPropane(TMP) of amount that are equivalent to hydroxyl 0.6 equivalent of polymkeric substance (B) are added.At last, 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, and stirs fully, obtains the diluting soln of tackiness composition.
In addition, the ratio of the monomer of cooperation, the amount of the hydroxyl among polymkeric substance (A) 100g (H[OH]) be 8.62mmol, the amount of the hydroxyl among polymkeric substance (B) 20g (L[OH]) be 25.84mmol.Therefore, to the mole number of the hydroxyl in polymkeric substance (A) 100 mass parts, the mole number purpose of the hydroxyl in polymkeric substance (B) 20 mass parts is 3.00 than (L[OH]/H[OH]).
At this, table 1 is listed in the cooperation of described tackiness composition.In addition, in the table 1 details of the contracted notation etc. of record following shown in.
[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): with polymkeric substance (A) addition (mass parts) as (g)
The mole number of the hydroxyl that calculates
L[OH] (mmol): with the mole number of polymkeric substance (B) addition (mass parts) as the hydroxyl of (g) calculating
[isocyanates linking agent (C)]
XDI-TMP: the Xylene Diisocyanate affixture of TriMethylolPropane(TMP) (Mitsui Chemicals urethane company system, trade(brand)name " TAKENATE D-110N ")
TDI-TMP: the tolylene diisocyanate affixture of TriMethylolPropane(TMP) (Japanese polyurethane company system, trade(brand)name " CORONET-L ")
[silane coupling agent (D)]
KBM403:3-glycidyl ether propyl trimethoxy silicane (chemical industrial company of SHIN-ETSU HANTOTAI system, trade(brand)name " KBM403 ")
Diluting soln with the tackiness composition that obtains, carried out stripping film (Lindeke Co., Ltd's system of lift-off processing with the type siloxane stripper at a face of pet film, SP-PET3811, thickness: lift-off processing face 38 μ m) carries out scraper for coating, making its dried thickness is 25 μ m, carry out 1 minute heat treated at 90 ℃, form adhering agent layer.
Then, to be consisted of by discoid polarizing film with liquid crystal layer, polarizing film and angle of visibility enlarge the integrated polarized light piece of film and fit, the exposing surface of adhering agent layer and the surface of discoid liquid crystal layer are joined, at 23 ℃, carry out maturation on the 7th under the 50%RH, obtain the polarized light piece with adhering agent layer.
(embodiment 2-10, comparative example 1-7)
Kind and ratio except each monomer that will consist of the 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), has similarly to Example 1 the manufacturing of adhering agent layer polarized light piece.
At this, above-mentioned weight average molecular weight (Mw) is to measure the weight average molecular weight of the polystyrene conversion of (GPC mensuration) by following condition with gel permeation chromatography (GPC).
＜condition determination 〉
GPC determinator: TOSOH company system, HLC-8020
GPC post (following order is passed through): TOSOH company system
TSK?guard?columN?HXL-H
TSK?gel?GMHXL(×2)
TSK?gel?G2000HXL
Measure solvent: tetrahydrofuran (THF)
Measure temperature: 40 ℃
(experimental example 1) (light leak experiment)
The polarized light piece with adhering agent layer that will obtain in embodiment or comparative example, (the wild super cutter of institute's company's system of making of reed PN1-600) is adjusted into 233mm * 309mm size with cutting device.Stripping film is peeled off, after the adhering agent layer that exposes is attached at non-alkali glass (Corning Incorporated's system, hawk XG), in the made still of the former making of fruit, with 0.5MPa, 50 ℃, pressurizeed 20 minutes.In addition, described applying, make the polarized light piece with adhering agent layer become polarizing axis is Niccol cross state (45 ° of polarizing axis: ∠, 135 ° of ∠).Under this state, after carrying out under the environment of 80 ℃ of dryings placing in 250 hours, 23 ℃, carry out under the environment of 50%RH placing in 2 hours, it is made sample, carry out the light leak evaluation with the method shown in following.The results are shown in table 2.
＜light leak evaluation: visual 〉
Described sample is arranged at flat head lamp (the logical industry company of electricity system, HF-SL-A312LC, illumination: 26,000Lux, briliancy: 10,000cd) on, (but the Buddhist nun blocks Minolta company system with two-dimentional color brightness photometer, CA-2000) scoop up shadow, (but the Buddhist nun blocks Minolta company system, CA-S20w) carries out the conversion of briliancy distributed image with resolving software.The briliancy distributed image of the sample that obtains is estimated by evaluation base Huaihe River shown in Figure 3.
(experimental example 2) (durability evaluation)
The polarized light piece with adhering agent layer that will obtain in embodiment or comparative example, (the wild super cutter of institute's company's system of making of reed PN1-600) is adjusted into 233mm * 309mm size with cutting device.Stripping film is peeled off, after the adhering agent layer that exposes is attached at non-alkali glass (Corning Incorporated's system, hawk XG), used the made still of the former making of chestnut at 0.5MPa, 50 ℃, pressurization in 20 minutes.
Afterwards, drop under the environment of following durable condition, observe with 10 times of magnifying glasses after 500 hours.Appearance change is observed with following basic Huaihe River.The results are shown in table 2.
◎: in 4 limits, no problem
In zero: 4 limit, the position no problem from peripheral end more than the 0.6mm
*: at least 1 limit on 4 limits, the position from peripheral end more than the 0.6mm is observed and is floated, and peels off foaming, the abnormal appearance of the tackiness agent that the 0.1mm of striped etc. is above
＜durable condition 〉
60 ℃, relative humidity 90%RH
(experimental example 3) (reusability evaluation)
To carry out severing at the polarized light piece with adhering agent layer that embodiment or comparative example obtain, it is wide to make 25mm, the sample that 100mm is long.From this sample stripping film is peeled off, between the adhering agent layer that exposes sample is pasted and pay in non-alkali glass (Corning Incorporated's system, hawk XG), thereafter, use the automatic still of company of the former making of fruit institute system at 0.5MPa, 50 ℃, carry out pressurization in 20 minutes.Then, carry out under the condition of 50 ℃ of dryings placing in 48 hours, 23 ℃, carry out damping in 3 hours under the condition of 50%RH.Afterwards, from non-alkali glass sample is peeled off with hand, visual valuation is carried out in the pollution on the surface of described non-alkali glass.Evaluation is carried out with following basic Huaihe River.The results are shown in table 2.
Zero: paneless pollution tackiness agent remaining
△: pollution tackiness agent remaining that few glass is only arranged
*: the pollution tackiness agent of glass remaining significantly
(experimental example 4) (evaluation of erosion resistance)
The stripping film of the polarized light piece with adhering agent layer that will obtain at embodiment or comparative example is peeled off, with Copper Foil (thickness: 80 μ m) fit after, 60 ℃, carry out keeping in 500 hours under the atmosphere of 90%RH.Afterwards, the polarized light piece that will have adhering agent layer from described Copper Foil is peeled off, and visual observation is carried out on the surface of the Copper Foil that exposes, and having or not of corrosion confirmed.The results are shown in table 2.
Zero: without corrosion
*: corrosion is arranged
(experimental example 5) (evaluation of mist degree (haze) value)
(thickness: the tectosome that 25 μ m) consists of (tectosome before polarized light piece attaches) in addition Huaihe River is standby for the stripping film/adhering agent layer that will obtain in the manufacturing processed of embodiment or comparative example.Fitted with soda-lime glass (mist degree (haze) value 0%) in the adhering agent layer surface that this tectosome exposes, stripping film is peeled off, make working sample.
With described working sample, (Japanese electric look industrial system NDH2000), is carried out mist degree (haze) value (%) (slightly being called Hz (%)) by JISK7105 and is measured with mist degree (haze) instrument.In addition, the scope of preferred mist degree (haze) value is 0-3%, is expressed as zero in this scope, described extraneous being expressed as *.The results are shown in table 2.
[table 1]
Table 1 (continuous 1)
Table 1 (continuous 2)
[table 2]
Can learn clearly that from table 2 in the polarized light piece with adhering agent layer that obtains in an embodiment, anti-light leak and weather resistance are all good, reusability, erosion resistance and optical characteristics are also good simultaneously
Tackiness composition of the present invention and tackiness agent, can be applicable to well optics, for example can be applicable to well the bonding of polarized light piece and polarizer, in addition, adhesive sheet of the present invention, adhesive sheet as the used for optical part that is used for polarized light piece and polarizer etc. can be suitable for well
[explanation of symbol]
1A, the 1B... adhesive sheet
11... adhering agent layer
12,12a, the 12b... stripping film
13... base material.
Claims (10)
1. tackiness composition is characterized in that:
Contain weight average molecular weight and be 500,000～3,000,000 the 1st (methyl) acrylic ester polymer (A), weight average molecular weight and be 8000～300,000 the 2nd (methyl) acrylic ester polymer (B) and linking agent (C),
Described the 1st (methyl) acrylic ester polymer (A) and described the 2nd (methyl) acrylic ester polymer (B) do not contain in fact acidic groups separately, and as the monomer unit that consists of described polymkeric substance, contain the hydroxyl monomer,
The hydroxyl monomer that the hydroxyl monomer that described the 1st (methyl) acrylic ester polymer (A) contains and described the 2nd (methyl) acrylic ester polymer (B) contain is one species,
The mol ratio of contained hydroxyl is 1.0～40 in described the 2nd (methyl) acrylic ester polymer (B) to hydroxyl contained in described the 1st (methyl) acrylic ester polymer (A).
2. tackiness composition according to claim 1 is characterized in that: described the 2nd (methyl) acrylic ester polymer (B), as the monomer unit that consists of this polymkeric substance, contain the described hydroxyl monomer of 10～40 quality %.
3. tackiness composition according to claim 1, it is characterized in that: for described the 1st (methyl) acrylic ester polymer (A) 100 mass parts, the ratio of described the 2nd (methyl) acrylic ester polymer (B) is 5～50 mass parts.
4. tackiness composition according to claim 1, it is characterized in that: described the 1st (methyl) acrylic ester polymer (A) and described the 2nd (methyl) acrylic ester polymer (B), except hydroxyl, do not contain in fact the functional group that has with responding property of described linking agent (C).
5. tackiness composition according to claim 1, it is characterized in that: described linking agent (C) is the isocyanates linking agent.
6. tackiness composition according to claim 5, it is characterized in that: the content of described isocyanates linking agent is, to the amount of the described hydroxyl that contains in described the 2nd (methyl) acrylic ester polymer (B), the isocyanate group of described isocyanates linking agent becomes the amount of 0.1～3.5 equivalent.
7. tackiness agent, it is crosslinked the forming of each described tackiness composition of request 1～6.
8. an adhesive sheet has base material and adhering agent layer, it is characterized in that: described adhering agent layer is made of tackiness agent claimed in claim 7.
9. adhesive sheet according to claim 8, it is characterized in that: described base material is optics.
10. adhesive sheet, the adhering agent layer that has 2 pieces of stripping films and seized on both sides by the arms by described stripping film, the release surface of described adhering agent layer and described 2 pieces of stripping films is joined thus, it is characterized in that, and described adhering agent layer is made of tackiness agent claimed in claim 7.
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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| Publication Number | Publication Date |
|---|---|
| CN102888203A true CN102888203A (en) | 2013-01-23 |
| CN102888203B 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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| Country | Link |
|---|---|
| JP (1) | JP5611129B2 (en) |
| KR (1) | KR101914457B1 (en) |
| CN (1) | CN102888203B (en) |
| TW (1) | TWI534225B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903789A (en) * | 2018-09-14 | 2020-03-24 | 日本电石工业株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
| CN115322693A (en) * | 2014-03-28 | 2022-11-11 | 琳得科株式会社 | Adhesive composition, adhesive and adhesive sheet |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2024050320A (en) * | 2022-09-29 | 2024-04-10 | 日東電工株式会社 | Adhesives and adhesive sheets |
| JP2024050319A (en) * | 2022-09-29 | 2024-04-10 | 日東電工株式会社 | Adhesives and adhesive sheets |
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| 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 |
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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
- 2012-05-17 TW TW101117517A patent/TWI534225B/en active
- 2012-06-18 KR KR1020120064937A patent/KR101914457B1/en active IP Right Grant
- 2012-06-28 CN CN201210224025.0A patent/CN102888203B/en active 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322693A (en) * | 2014-03-28 | 2022-11-11 | 琳得科株式会社 | Adhesive composition, adhesive and adhesive sheet |
| CN110903789A (en) * | 2018-09-14 | 2020-03-24 | 日本电石工业株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
| CN110903789B (en) * | 2018-09-14 | 2022-10-11 | 日本电石工业株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101914457B1 (en) | 2018-11-02 |
| TWI534225B (en) | 2016-05-21 |
| TW201307502A (en) | 2013-02-16 |
| CN102888203B (en) | 2016-02-17 |
| JP5611129B2 (en) | 2014-10-22 |
| KR20130002265A (en) | 2013-01-07 |
| JP2013010837A (en) | 2013-01-17 |
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