CN103571358A - Protective film - Google Patents

Protective film Download PDF

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Publication number
CN103571358A
CN103571358A CN201310327385.8A CN201310327385A CN103571358A CN 103571358 A CN103571358 A CN 103571358A CN 201310327385 A CN201310327385 A CN 201310327385A CN 103571358 A CN103571358 A CN 103571358A
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Prior art keywords
methyl
molecular weight
telluro
mentioned
protective membrane
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CN201310327385.8A
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CN103571358B (en
Inventor
黑川敦史
荒井隆行
所司悟
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Lintec Corp
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Lintec Corp
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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]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a protective film having an adhesive layer, wherein the adhesive layer consists of an adhesive composition containing (methyl) acrylate copolymer (A), isocyanate cross-linking agent (B) and organo-tin compound (C), the (methyl) acrylate copolymer (A) is the copolymer which is obtained by living free radical polymerization and has a weight-average molecular weight (Mw) ranging from 40 to 200 ten thousand and a molecular weight distribution (Mw/Mn) value lower than 2.5, the (methyl) acrylate copolymer (A) also contains Te metal, the ratio between the organo-tin compound (C) in the adhesive composition and the Te metal ranges from 2:1 to 20:1 by mass. According to the present invention, provided is the protective film having the adhesive layer, which can be bonded to an adherend with sufficient adhesive force when being bonded the adherend and has little residue attached to the adherend when being peeled off.

Description

Protective membrane
Technical field
The present invention relates to a kind of protective membrane with binder layer.More specifically, relate to residual monomer in a kind of binder composition that forms binder layer and low molecular weight compositions few and be attached to the few protective membrane of residue thing of adherend.
Background technology
At present; for objects such as the anti-glare with headed by surface protection, antireflections; protective membrane is used to various image display devices as optical applications, such as LCD (liquid crystal display), touch panel, CRT (cathode-ray picture tube), PDP (plasma display), EL (electroluminescent) indicating meter, optical recording medium etc.In addition, in LCD, protective membrane is used to protect polarizer.With regard to this protective membrane, conventionally in the one side of matrix material film, there is binder layer, on another side, be provided with the functional coats such as antistatic property, antifouling property or be provided with as required hard coat etc.
In addition, because optical characteristics is excellent, the design of tackiness agent is easier to, therefore, in above-mentioned binder layer, used and take the acrylic adhesives that (methyl) acrylic acid esters co-polymer is host.Known when the protective membrane with such binder layer is fitted in to described adherend via binder layer, can on adherend, with the beyond all recognition level of vision, adhere to a little residue thing.Can think, in the situation that using acrylic adhesives, this residue thing results from residual monomer, the low molecular weight compositions existing in (methyl) acrylic acid esters co-polymer as host.
The acrylic acid or the like pressure-sensitive caking agent that a kind of low molecular weight compositions is few is disclosed in patent documentation 1, but with regard to its residue thing adhesion amount reduces effect, still insufficient.
On the other hand, in macromolecular polymerization reaction, as meeting, carry out growth response but the polymerization of termination reaction, chain transfer reaction can not occur, known have an active free radical polymerization.That is, it is active that the growth end of reactive polymer, the polymkeric substance that is polymerized by living polymerization still keeps after consuming monomer, if append monomer, understands initiated polymerization again.Hence one can see that, and the molecular weight of polymkeric substance can increase pro rata with monomer consumption, can obtain molecular weight homogeneous, be the polymkeric substance of narrow molecular weight distribution.
On the other hand, in radical polymerization, the life-span of growth free radical is extremely short, has the such polymerization of bimolecular termination reaction and stops mechanism.Therefore, thought to carry out the living polymerization of free radical, but in recent years in the past, though self-discovery also after stable free radical, started to carry out energetically the research of active free radical polymerization, and developed the whole bag of tricks under air exists.
For example, a kind of use Organic Tellurium Compounds is disclosed in patent documentation 2 and 3 as active free radical polymerization initiator, by polymerization of vinyl monomer, thus the technology of the living-radical polymers of manufacture molecular weight homogeneous.
Following content is disclosed in patent documentation 4: by adopting above-mentioned active free radical polymerization; can make molecular weight is that low molecular weight compositions below 50,000 reaches below 5 quality %; but because the Organic Tellurium Compounds for polymerization starter can work as the paralyser of linking agent, therefore can cause the crosslinked delay of binder composition and in the protective membrane that comprises the binder layer being formed by above-mentioned binder composition, produce through time the re-separation that causes.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-214142 communique
Patent documentation 2: TOHKEMY 2006-299278 communique
Patent documentation 3:WO2004/014962 brochure
Patent documentation 4: TOHKEMY 2011-74380 communique
Summary of the invention
The problem that invention will solve
The present invention completes based on above-mentioned background; object is to provide a kind of protective membrane; even if described protective membrane is in the situation that select (methyl) acrylic acid esters co-polymer as the host in binder composition; when the protective membrane with the binder layer being formed by described binder composition is fitted in to various adherend; also can give play to sufficient bounding force, and when peeling off, be attached to adherend to result from the residue thing of described binder composition few.
The method of dealing with problems
The inventor etc. conduct in-depth research in order to achieve the above object, found that following content.
Find; the protective membrane with the binder layer being formed by following binder composition can be realized above-mentioned purpose; described binder composition selects (methyl) acrylic acid esters co-polymer with specific trait of obtaining by active free radical polymerization as the host of binder composition, and this binder composition contains this multipolymer, isocyanates linking agent and with respect to tellurium metal contained in described multipolymer, be the organo-tin compound of regulation ratio.The present invention is based on the recognition opinion and completes.
That is, the invention provides:
[1] a kind of protective membrane, it has the binder layer being formed by binder composition, described binder composition comprise the weight-average molecular weight obtaining by active free radical polymerization be 400,000～2,000,000 and molecular weight distribution lower than 2.5 (methyl) acrylic acid esters co-polymer (A), isocyanates linking agent (B) and organo-tin compound (C), wherein, with respect to the tellurium metal containing in described (A), contain 2～20 quality described organo-tin compound (C) doubly;
[2], according to above-mentioned [1] described protective membrane, wherein, the ratio that the middle weight-average molecular weight of (methyl) acrylic acid esters co-polymer (A) is the low molecular weight compositions below 100,000 is lower than 5 quality %; And
[3], according to above-mentioned [1] or [2] described protective membrane, it is in the one side of plastic film, have binder layer and form at the stacked release sheet of face side that exposes of described binder layer.
In addition, the present invention includes following aspect.
<1> protective membrane; it has binder layer; wherein; described binder layer is formed by the binder composition that comprises (methyl) acrylic acid esters co-polymer (A), isocyanates linking agent (B) and organo-tin compound (C); described (methyl) acrylic acid esters co-polymer (A) is that the weight-average molecular weight (Mw) that obtains by active free radical polymerization is 400,000～2,000,000, molecular weight distribution (Mw/Mn) value is lower than 2.5 multipolymer
Described (methyl) acrylic acid esters co-polymer (A) also contains tellurium metal,
Described organo-tin compound (C) in described binder composition and the ratio of described tellurium metal are 2:1～20:1 by quality ratio;
<2> is according to the protective membrane described in <1>, wherein, with respect to the total mass of described (methyl) acrylic acid esters co-polymer (A), the ratio that the middle weight-average molecular weight of described (methyl) acrylic acid esters co-polymer (A) is the low molecular weight compositions below 100,000 is lower than 5 quality %;
<3> protective membrane, it is the protective membrane described in <1> or <2>, it also comprises release sheet,
Described binder layer is layered at least simultaneously upper of described plastic film,
Described release sheet is layered on described binder layer.
The effect of invention
According to the present invention, can provide a kind of can be to be adhered to adherend and to be attached to the few protective membrane with binder layer of residue thing of adherend when peeling off in order to reach the sufficient bounding force of protection object when fitting in adherend.The function that this protective membrane can suppress to cause because of adhering to of residue thing reduces, and therefore, can be applied to require with high level the functional optical components of surface cleanliness.In addition, by the ratio with regulation in binder composition, contain organo-tin compound, can improve and in existing formula, become the crosslinked delay of the binder composition of problem and the re-separation of protective membrane.
At this, described " bounding force fully " refers to that the bounding force of protective membrane is more than 50mN/25mm.In addition, the peeling force that described " re-separation " refers to release sheet through time increase astatically.
Embodiment
Protective membrane of the present invention is the protective membrane with binder layer, wherein, above-mentioned binder layer is by comprising (methyl) acrylic acid esters co-polymer (A), the binder composition of isocyanates linking agent (B) and organo-tin compound (C) forms, above-mentioned (methyl) acrylic acid esters co-polymer (A) is that the weight-average molecular weight (Mw) obtaining by active free radical polymerization is 400,000～2,000,000, molecular weight distribution (Mw/Mn) is worth the multipolymer lower than 2.5, above-mentioned (methyl) acrylic acid esters co-polymer (A) also contains tellurium metal, above-mentioned organo-tin compound (C) in above-mentioned binder composition and the ratio of above-mentioned tellurium metal are 2:1～20:1 by quality ratio.
< binder composition >
Protective membrane of the present invention has the binder layer being formed by binder composition, and above-mentioned binder composition contains that the weight-average molecular weight obtaining by active free radical polymerization is 400,000～2,000,000, molecular weight distribution (Mw/Mn) value is lower than 2.5 multipolymer i.e. (methyl) acrylic acid esters co-polymer (A), isocyanates linking agent (B) and organo-tin compound (C).In addition, in one embodiment of the present invention, preferred above-mentioned binder composition also contains solvent except mentioned component.Below, each composition in binder composition is described.
[(methyl) acrylic acid esters co-polymer (A)]
(methyl) acrylic acid esters co-polymer (A) is the composition containing as host in the binder composition of the binder layer in forming protective membrane of the present invention, has proterties as follows.At this, described " host " refers to that the total mass (solids component scaled value) with respect to binder composition contains that 50 quality % are above, preferred above, the composition more than 90 quality % particularly preferably of 80 quality %.In addition, its upper limit is not particularly limited, except the residual ratio that linking agent (B) and organo-tin compound (C) etc. are of the present invention must composition is the upper limit.It should be noted that, above-mentioned " (methyl) acrylate " refer to acrylate and methacrylic ester the two.Other similar term is also identical.
(proterties of composition (A))
Require the weight-average molecular weight (Mw) of (methyl) acrylic acid esters co-polymer (A) in 400,000～2,000,000 scope, the value of molecular weight distribution (ratio of weight-average molecular weight (Mw)/number-average molecular weight (Mn)) is lower than 2.5.If the weight-average molecular weight of mentioned component (A) is lower than 400,000, weight-average molecular weight is that one-tenth component below 100,000 must increase, and cannot prevent residue thing adhering on adherend.On the other hand, if the Mw of composition (A) surpasses 2,000,000, can cause because of the viscosity rise of composition (A) the smoothness variation of applicator surface.In addition, in order to suppress such viscosity, increase a large amount of solvent of needs, from the viewpoint of manufacturing cost, consider, or aspect environmental practice, all not preferred.In addition, if the weight-average molecular weight of composition (A) is greater than 2,000,000, when polymerization is carried out, the control of growth response becomes insufficient sometimes, and molecular weight distribution expands.
; if the Mw of composition (A) in 400,000～2,000,000 scope, can prevent that residue thing from adhering to adherend, and easily the applicator surface smoothness variation causing because of viscosity rise and cost rising are suppressed; be easy to control molecular weight distribution, therefore preferably.
In addition, if consider, residue thing is few, adhesion durability and coating adaptability etc., the weight-average molecular weight of composition (A) preferably 500,000～1,500,000, more preferably 850,000～1,200,000.At this, described " adhesion durability " refers to following performance: even fitting under the state on the adherends such as glass and preserving the specified time under hot conditions or under wet heat condition, and the performance that binder layer can not produce perk (floating I) yet, peel off.In addition, described " coating adaptability " refers to following performance: the solvability in solvent is excellent, even if do not use a large amount of solvents also can form level and smooth applicator surface.
In addition, the molecular weight distribution of composition (A) (Mw/Mn ratio) value is preferably lower than 2.5.If the molecular weight distribution value of composition (A) is more than 2.5, be difficult to realize the minimizing of low molecular weight compositions in described (methyl) acrylic acid esters co-polymer (A) described later, sometimes cannot realize object of the present invention.Therefore, preferred molecular weight distribution (Mw/Mn ratio) is lower than 2.5.Be particularly preferably 1.0～2.2.
In addition,, in above-mentioned (methyl) acrylic acid esters co-polymer (A), with respect to the total mass of composition (A), weight-average molecular weight (Mw) is that the ratio of the low molecular weight compositions below 100,000 is preferably lower than 5 quality %.That is, in the present invention, described " low molecular weight compositions " refers to that Mw is the component of polymer below 100,000.If the ratio of this low molecular weight compositions is more than 5 quality % with respect to composition (A) total mass; in the situation that use the protective membrane of the binder layer that the binder composition contain composition (A) forms to be fitted on adherend via above-mentioned binder layer by having, sometimes cannot by residue thing, adhering on above-mentioned adherend be suppressed at enough low level.That is,, if the ratio of contained low molecular weight compositions is with respect to the total mass of composition (A) lower than 5 quality % in composition (A), while peeling off protective membrane of the present invention from adherend, the residue thing on adherend adheres to and tails off, therefore preferably.
Therefore, weight-average molecular weight is that the ratio of the low molecular weight compositions below 100,000 is more preferably below 3 quality % with respect to the total mass of composition (A), more preferably, below 2 quality %, is particularly preferably below 1 quality %.In addition, the lower value of the low molecular weight compositions in composition (A) is not particularly limited, if consider manufacturing cost etc., with respect to the total mass of composition (A), is preferably more than 0.01 quality %, more preferably more than 0.05 quality %.
It should be noted that, the ratio of above-mentioned low molecular weight compositions, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are the polystyrene standard scaled values recording by gel permeation chromatography (GPC) method.
In addition, the residue thing adhesion amount on adherend can be by utilizing the numbers of unremovable particle test that laser surface test set is measured the retained foreign body number on adherend surface to obtain.
(composition of composition (A))
Above-mentioned (methyl) acrylic acid esters co-polymer (A) preferably contains (methyl) acrylate monomeric units (a) (below also referred to as non-functional monomer unit (a)) with ester residue and (methyl) acrylate monomeric units (b) (below also referred to as functional monomer unit (b)) with reactive functional groups in the ratio of mass ratio (non-functional monomer unit (a): functional monomer unit (b)) 80:20～99.9:0.1, wherein, the alkyl that above-mentioned ester residue is carbonatoms 1～20.Reactive functional groups in above-mentioned functional monomer unit (b) is to become the functional group that carries out crosslinked cross-linking set by aftermentioned linking agent.Therefore, by the total amount of above-mentioned functional monomer unit (b) and above-mentioned non-functional monomer unit (a), be that the total amount of non-functional monomer unit (a) contained in the structure of composition (A) and functional monomer unit (b) is while being made as 100 quality %, if the content of above-mentioned functional monomer unit (b) is lower than 0.1 quality %, the cross-linking set of above-mentioned (methyl) acrylic acid esters co-polymer (A) tails off, and likely cannot be cross-linked fully by aftermentioned linking agent.Therefore the binder composition that, contains such composition (A) likely becomes bounding force, the poor material of adhesion durability.From the viewpoint, preferably with respect to the total amount (100 quality %) of non-functional monomer unit (a) and functional monomer unit (b), the content of above-mentioned functional monomer unit (b) is more than 0.5 quality %, more than being particularly preferably 1 quality %.
On the other hand, if the content of above-mentioned functional monomer unit (b) surpasses 20 quality %, during the binder composition that contains composition (A) in manufacture, easily cause gelation.And then, likely cause the problem too short and initiation operability that becomes working life (pot life) after composition (A) adds linking agent.In addition, also likely cause the cohesive force of gained tackiness agent to become too high and cause that bounding force reduces, the adaptation variation to adherend.From the viewpoint, further the content of preferred above-mentioned functional monomer unit (b) is below 10 quality %.
In addition, there is the situation that is coordinated in radical initiator (Organic Tellurium Compounds) in the functional group of functional monomer unit (b), the viewpoint of controlling the inadequate hidden danger that becomes from eliminating polymerization, particularly preferably the content of functional monomer unit (b) is below 8 quality %.
Above-mentioned (methyl) acrylic acid esters co-polymer (A) can be by making to form (methyl) acrylate that the alkyl with carbonatoms 1～20 of above-mentioned non-functional monomer unit (a) is ester residue, form (methyl) acrylate with reactive functional groups of above-mentioned functional monomer unit (b) and as required and other monomer of use carries out copolymerization manufactures.
As thering is the example that alkyl carbon atoms number is (methyl) acrylate of 1～20 ester residue, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid stearyl etc.These may be used alone, can also be used in combination two or more.
On the other hand, as the example with (methyl) acrylate of reactive functional groups, can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid monomethyl amino ethyl ester, (methyl) vinylformic acid list ethylamino ethyl ester, the amino propyl ester of (methyl) vinylformic acid monomethyl, (methyl) vinylformic acid alkyl monosubstituted amino alkyl esters such as (methyl) vinylformic acid list ethylamino propyl ester etc.These may be used alone, can also be used in combination two or more uses, in the present invention, from viewpoints such as bridging properties, consider, preferably use (methyl) vinylformic acid hydroxyalkyl acrylate.
In addition, as the example of other monomer using as required, can enumerate: the vinyl esters such as vinyl-acetic ester, propionate; The olefines such as ethene, propylene, iso-butylene; The haloalkene such as vinylchlorid, vinylidene chloride hydro carbons; The styrene monomer such as vinylbenzene, alpha-methyl styrene; The dienes monomers such as divinyl, isoprene, chloroprene; The nitrile monomer such as vinyl cyanide, methacrylonitrile; The acrylic amides such as acrylamide, N methacrylamide, N,N-DMAA etc.These may be used alone, can also be used in combination two or more uses.
As above-mentioned (methyl) acrylic acid esters co-polymer (A), the bond properties excellence of the bonding coat forming from the viewpoint of the binder composition by containing mentioned component (A), the multipolymer preferably being formed by butyl acrylate and vinylformic acid 4-hydroxyl butyl ester, by butyl acrylate, the multipolymer that 2-EHA and vinylformic acid 4-hydroxyl butyl ester form, the multipolymer being formed by butyl acrylate and vinylformic acid 2-hydroxy methacrylate, by butyl acrylate, the multipolymer that cyclohexyl acrylate and vinylformic acid 4-hydroxyl butyl ester form, or by butyl acrylate, the multipolymer that methyl acrylate and vinylformic acid 4-hydroxyl butyl ester form.
In the multipolymer being obtained by above-mentioned preferably combination, become cross-linking set vinylformic acid 4-hydroxyl butyl ester unit or vinylformic acid 2-hydroxy methacrylate unit, be the content of functional monomer unit (b), preferably the total amount (100 quality %) with respect to above-mentioned non-functional monomer unit (a) and functional monomer unit (b) is 0.5～10 quality % left and right, is particularly preferably 1～8 quality %.
(manufacture method of composition (A))
Above-mentioned (methyl) acrylic acid esters co-polymer (A) is to carry out by active free radical polymerization the multipolymer that polymerization obtains.Active free radical polymerization is compared with radical polymerization, and the reaction with active site place is feature very slowly.That is, in radical polymerization, the reaction at active site place is very fast, and therefore it is generally acknowledged from hyperergy monomer and start polymerization, then, reactive low monomer generation polymerization.On the other hand, in active free radical polymerization, due to the sluggish at active site place, therefore can think that it is not subject to the impact of reactwity of monomer, carry out equably polymerization, any multipolymer obtaining is all realized more impartial composition.Can think thus, (methyl) acrylic acid esters co-polymer (A) obtaining by active free radical polymerization and the polymer phase ratio obtaining by radical polymerization, the generation ratio of (methyl) esters of acrylic acid homopolymer only consisting of non-functional monomer unit (a) significantly reduces.So, even in the situation that the weight-average molecular weight of (methyl) acrylic acid esters co-polymer (A) obtaining by active free radical polymerization is low, for example, in the situation that Mw is 400,000 left and right, by aftermentioned linking agent (B), there is crosslinked possibility and also become very high.Its result; can think to have by take the protective membrane of the present invention of the binder layer that binder composition that (methyl) acrylic acid esters co-polymer (A) of obtaining by active free radical polymerization is host forms and the residue thing on adherend can be adhered to the low-down level that is suppressed at.
Manufacture method as composition (A), can adopt existing known active free radical polymerization method, such as the Transfer Radical Polymerization of using atom transfer radical polymerization agent as polymerization control agent (ATRP polymerization), the polymerization (RAFT polymerization) utilizing reversible addition-fracture chain-transfer agent to carry out reversible addition-fracture chain to shift, use Organic Tellurium Compounds as the polymerization of polymerization starter etc.In these living radical polymerizations, from molecular weight control and also can polymerization water system etc. aspect consider, preferably use Organic Tellurium Compounds as the method for polymerization starter.Below, to using machine tellurium compound to describe as the method for polymerization starter.
The active free radical polymerization > of the composition (A) that < use Organic Tellurium Compounds carries out
Above-mentioned (methyl) acrylic acid esters co-polymer (A) can be by comprising that the method for following operation (polymerization process) manufactures, and described operation (polymerization process) is to use active free radical polymerization initiator (below also referred to as Organic Tellurium Compounds I) that for example following general formula (1) represents to make the operation of monomer mixture polymerization.
[Chemical formula 1]
Figure BDA00003597200500081
[in formula, R 1the alkyl, aryl, substituted aryl or the aromatic heterocycle that represent carbonatoms 1～8.R 2and R 3the alkyl that represents hydrogen atom or carbonatoms 1～8.R 4represent aryl, substituted aryl, aromatic heterocycle, acyl group, oxygen carbonyl or cyano group.]
R 1described in shown group is specific as follows.
As the alkyl of carbonatoms 1～8, can enumerate: the straight chain shape of the carbonatomss 1～8 such as methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, sec-butyl, the tertiary butyl, cyclobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, chain or cyclic alkyl.As alkyl, the alkyl of the straight chain shape of preferred carbonatoms 1～4 or a chain, more preferably methyl or ethyl.
As aryl, can enumerate: phenyl, naphthyl etc.; As substituted aryl, can enumerate: there is substituent phenyl, there is substituent naphthyl etc.; As aromatic heterocycle, can enumerate: pyridyl, furyl, thienyl etc.As the above-mentioned substituting group with substituent aryl, for example can enumerate: halogen atom, hydroxyl, alkoxyl group, amino, nitro, cyano group ,-COR 5shown carbonyl group-containing groups (R 5the alkyl of=carbonatoms 1～8, aryl, the alkoxyl group of carbonatoms 1～8, aryloxy), alkylsulfonyl, trifluoromethyl etc.As preferred aryl, can enumerate: phenyl, trifluoromethyl substituted-phenyl.In addition, these substituting groups can replace one or two, and preferably contraposition or ortho position replace.
R 2and R 3described in each group of representing is specific as follows.
As the alkyl of carbonatoms 1～8, can enumerate: with above-mentioned R 1the group that shown alkyl is same.
R 4described in each shown group is specific as follows.
As aryl, substituted aryl, aromatic heterocycle, can enumerate: with above-mentioned R 1the group that shown group is same.
As acyl group, can enumerate: formyl radical, ethanoyl, benzoyl etc.
As oxygen carbonyl, preferably-COOR 6(R 6=H, the alkyl of carbonatoms 1～8, aryl) shown in group, can enumerate such as carboxyl, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, n-butoxy carbonyl, sec-butoxy carbonyl, tert-butoxycarbonyl, n-pentyloxy carbonyl, phenyloxycarbonyl etc.As preferred oxygen carbonyl, can enumerate: methoxycarbonyl, ethoxy carbonyl.
As R 4each shown group, can preferably enumerate: aryl, substituted aryl, oxygen carbonyl.As preferred aryl, can enumerate phenyl.As preferred substituted aryl, can enumerate: halogen atom substituted-phenyl, trifluoromethyl substituted-phenyl.In addition, in the situation that these substituting groups are halogen atom, can enumerate: replace the group of 1～5.In the situation that these substituting groups are alkoxyl group, trifluoromethyl, can enumerate: replace 1 or 2 s' group, in the situation that replacing 1, preferably contraposition or ortho position replace, in the situation that replacing 2, preferably between position replace.As preferred oxygen carbonyl, can enumerate: methoxycarbonyl, ethoxy carbonyl.
Organic Tellurium Compounds I as shown in general formula (1), can preferably enumerate: R 1the alkyl, the R that represent carbonatoms 1～4 2and R 3the alkyl, the R that represent hydrogen atom or carbonatoms 1～4 4the compound representing during for aryl, substituted aryl, oxygen carbonyl.Can particularly preferably enumerate: R 1the alkyl, the R that represent carbonatoms 1～4 2and R 3the alkyl, the R that represent hydrogen atom or carbonatoms 1～4 4for phenyl, the compound representing when substituted-phenyl, methoxycarbonyl, ethoxy carbonyl.
Described in Organic Tellurium Compounds shown in general formula (1) is specific as follows.
As Organic Tellurium Compounds, can enumerate: (methyl telluro-methyl) benzene, (1-methyl telluro-ethyl) benzene, (2-methyl telluro-propyl group) benzene, the chloro-4-of 1-(methyl telluro-methyl) benzene, 1-hydroxyl-4-(methyl telluro-methyl) benzene, 1-methoxyl group-4-(methyl telluro-methyl) benzene, 1-amino-4-(methyl telluro-methyl) benzene, 1-nitro-4-(methyl telluro-methyl) benzene, 1-cyano group-4-(methyl telluro-methyl) benzene, 1-methyl carbonyl-4-(methyl telluro-methyl) benzene, 1-phenylcarbonyl group-4-(methyl telluro-methyl) benzene, 1-methoxycarbonyl-4-(methyl telluro-methyl) benzene, 1-phenyloxycarbonyl-4-(methyl telluro-methyl) benzene, 1-alkylsulfonyl-4-(methyl telluro-methyl) benzene, 1-trifluoromethyl-4-(methyl telluro-methyl) benzene, the chloro-4-of 1-(1-methyl telluro-ethyl) benzene, 1-hydroxyl-4-(1-methyl telluro-ethyl) benzene, 1-methoxyl group-4-(1-methyl telluro-ethyl) benzene, 1-amino-4-(1-methyl telluro-ethyl) benzene, 1-nitro-4-(1-methyl telluro-ethyl) benzene, 1-cyano group-4-(1-methyl telluro-ethyl) benzene, 1-methyl carbonyl-4-(1-methyl telluro-ethyl) benzene, 1-phenylcarbonyl group-4-(1-methyl telluro-ethyl) benzene, 1-methoxycarbonyl-4-(1-methyl telluro-ethyl) benzene, 1-phenyloxycarbonyl-4-(1-methyl telluro-ethyl) benzene, 1-alkylsulfonyl-4-(1-methyl telluro-ethyl) benzene, 1-trifluoromethyl-4-(1-methyl telluro-ethyl) benzene [or being called 1-(1-methyl telluro-ethyl)-4-trifluoromethylbenzene], 1-(1-methyl telluro-ethyl)-3,5-dual-trifluoromethyl benzene, the fluoro-6-of 1,2,3,4,5-five (1-methyl telluro-ethyl) benzene, the chloro-4-of 1-(2-methyl telluro-propyl group) benzene, 1-hydroxyl-4-(2-methyl telluro-propyl group) benzene, 1-methoxyl group-4-(2-methyl telluro-propyl group) benzene, 1-amino-4-(2-methyl telluro-propyl group) benzene, 1-nitro-4-(2-methyl telluro-propyl group) benzene, 1-cyano group-4-(2-methyl telluro-propyl group) benzene, 1-methyl carbonyl-4-(2-methyl telluro-propyl group) benzene, 1-phenylcarbonyl group-4-(2-methyl telluro-propyl group) benzene, 1-methoxycarbonyl-4-(2-methyl telluro-propyl group) benzene, 1-phenyloxycarbonyl-4-(2-methyl telluro-propyl group) benzene, 1-alkylsulfonyl-4-(2-methyl telluro-propyl group) benzene, 1-trifluoromethyl-4-(2-methyl telluro-propyl group) benzene, 2-(methyl telluro-methyl) pyridine, 2-(1-methyl telluro-ethyl) pyridine, 2-(2-methyl telluro-propyl group) pyridine, 2-methyl-2-methyl telluro-propionic aldehyde, 3-methyl-3-methyl telluro-2-butanone, 2-methyl telluro-methyl acetate, 2-methyl telluro-methyl propionate, 2-methyl telluro-2 Methylpropionic acid methyl esters, 2-methyl telluro-ethyl acetate, 2-methyl telluro-ethyl propionate, 2-methyl telluro-2 Methylpropionic acid ethyl ester [or being called 2-methyl-2-methyl telluro-ethyl propionate], 2-(normal-butyl telluro)-2 Methylpropionic acid ethyl ester [or being called 2-methyl-2-normal-butyl telluro-ethyl propionate], 2-methyl telluro acetonitrile, 2-methyl telluro propionitrile, 2-methyl-2-methyl telluro propionitrile, (phenyl telluro-methyl) benzene, (1-phenyl telluro-ethyl) benzene, (2-phenyl telluro-propyl group) benzene etc.
In addition, in above-mentioned, methyl telluro, 1-methyl telluro, 2-methyl telluro part changed to respectively to the compound that ethyl telluro, 1-ethyl tellurium, 2-ethyl telluro, butyl telluro, 1-butyl telluro, 2-butyl telluro form and be also all included in wherein.Can preferably enumerate: (methyl telluro-methyl) benzene, (1-methyl telluro-ethyl) benzene, (2-methyl telluro-propyl group) benzene, the chloro-4-of 1-(1-methyl telluro-ethyl) benzene, 1-trifluoromethyl-4-(1-methyl telluro-ethyl) benzene [1-(1-methyl telluro-ethyl)-4-trifluoromethylbenzene], 2-methyl telluro-2 Methylpropionic acid methyl esters, 2-methyl telluro-2 Methylpropionic acid ethyl ester [2-methyl-2-methyl telluro-ethyl propionate], 2-(normal-butyl tellurium)-2 Methylpropionic acid ethyl ester [2-methyl-2-normal-butyl telluro-ethyl propionate], 1-(1-methyl telluro-ethyl)-3,5-dual-trifluoromethyl benzene, the fluoro-6-of 1,2,3,4,5-five (1-methyl telluro-ethyl) benzene, 2-methyl telluro propionitrile, 2-methyl-2-methyl telluro propionitrile, (ethyl telluro-methyl) benzene, (1-ethyl telluro-ethyl) benzene, (2-ethyl telluro-propyl group) benzene, 2-ethyl telluro-2 Methylpropionic acid methyl esters, 2-ethyl telluro-2 Methylpropionic acid ethyl ester, 2-ethyl telluro propionitrile, 2-methyl-2-ethyl telluro propionitrile, (normal-butyl telluro-methyl) benzene, (1-normal-butyl telluro-ethyl) benzene, (2-normal-butyl telluro-propyl group) benzene, 2-normal-butyl telluro-2 Methylpropionic acid methyl esters, 2-normal-butyl telluro-2 Methylpropionic acid ethyl ester, 2-normal-butyl telluro propionitrile, 2-methyl-2-normal-butyl telluro propionitrile.
Organic Tellurium Compounds shown in these general formulas (1) can be used separately a kind of, also can be used in combination two or more.Wherein, from meet the viewpoint of polymerization velocity and molecular weight control simultaneously, consider, preferably use 2-methyl-2-normal-butyl telluro-ethyl propionate, 2-normal-butyl telluro-2 Methylpropionic acid methyl esters or (normal-butyl telluro-methyl) benzene.
In one embodiment of the present invention, as the above-mentioned polymerization process in the manufacture method of composition (A), can be except above-mentioned Organic Tellurium Compounds, adding azo is as required that polymerization starter carries out as polymerization promotor.As azo, be polymerization starter, so long as conventionally can be used for the initiator of radical polymerization, in thering is the scope of effect of the present invention, be not particularly limited.Particularly, can enumerate: 2, 2'-Diisopropyl azodicarboxylate (AIBN), 2, 2'-azo two (2-methylbutyronitrile) (AMBN), 2, 2'-azo two (2, 4-methyl pentane nitrile) (ADVN), 1, 1'-azo two (1-hexanaphthene formonitrile HCN) (ACHN), dimethyl-2, 2'-azo-bis-isobutyrate (MAIB), 4, 4'-azo two (4-cyanopentanoic acid) (ACVA), 1, 1'-azo two (1-acetoxyl group-1-diphenylphosphino ethane), 2, 2'-azo two (2-methyl butyl acid amides), 2, two (4-methoxyl group-2 of 2'-azo, 4-methyl pentane nitrile), 2, two (the 2-methyl amidine propane) dihydrochlorides of 2'-azo, 2, 2'-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2, 2'-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2, 2'-azo two (2, 4, 4-trimethylpentane), 2-cyano group-2-propyl group azoformamide, 2, 2'-azo two (N-butyl-2-methyl propanamide), 2, 2'-azo two (N-cyclohexyl-2-methyl propanamide) etc.
By above-mentioned azo, be that polymerization starter and above-mentioned Organic Tellurium Compounds are be used in combination in the situation that, with respect to the Organic Tellurium Compounds 1mol as the above-mentioned general formula (1) of polymerization starter, preferably with 0.01～100mol, more preferably with 0.1～100mol, further preferably with the ratio of 0.1～5mol, to use above-mentioned azo be polymerization starter.
By active free radical polymerization manufacture the method for above-mentioned (methyl) acrylic acid esters co-polymer (A) specific as follows described in.
In the container with after inactive gas displacement, mixing mixture, the active free radical polymerization initiator (Organic Tellurium Compounds) shown in general formula (1) of above-mentioned monomer and the azo using is as required polymerization starter.Now, as inactive gas, can enumerate: nitrogen, argon, helium etc.Preferably enumerate argon, nitrogen.Particularly preferably enumerate nitrogen.
Usage quantity as the active free radical polymerization initiator (Organic Tellurium Compounds) shown in general formula (1) with respect to monomer, as long as according to target weight-average molecular weight or the suitable adjusting of molecular weight distribution value of (methyl) acrylic acid esters co-polymer (A).As preferred usage quantity, roughly be preferably value that summation that molecular weight with each monomer is multiplied by the value that pan feeding ratio obtains obtains divided by the weight-average molecular weight (Mw) of target multipolymer (A) (here, the usage quantity of Organic Tellurium Compounds represents with " mol "), according to above-mentioned weight-average molecular weight, the amount of 0.3～3 of above-mentioned value times of left and right more preferably.
In the manufacture method of composition (A), above-mentioned polymerization process carries out conventionally under solvent-free, also can in radical polymerization, in normally used organic solvent, carry out.As spendable solvent, can enumerate such as benzene, toluene, DMF (DMF), methyl-sulphoxide (DMSO), acetone, chloroform, tetracol phenixin, tetrahydrofuran (THF) (THF), ethyl acetate, phenylfluoroform etc.In addition, also can use aqueous solvent, can enumerate such as water, methyl alcohol, ethanol, Virahol, propyl carbinol, ethyl cellosolve, ethylene glycol butyl ether, 1-methoxy-2-propanol etc.As the usage quantity of solvent, as long as suitable adjusting is preferably for example 0.01～100ml with respect to monomer 1g, more preferably 0.05～10ml, is particularly preferably 0.05～0.5ml.
Then, while stir the polymerization that said mixture carries out composition (A).As long as polymerization temperature and reaction times, according to the target weight-average molecular weight of composition (A) or the suitable adjusting of molecular weight distribution, preferably stir 5～100 hours conventionally at 60～150 ℃.In addition, also can preferably at 80～120 ℃, stir 10～30 hours.Now, with regard to pressure, conventionally under normal pressure, carry out, under also can pressurizeing in the scope of 0.01～10MPa or reduce pressure, carry out.
Preferably after reaction finishes, carry out as required purification procedures, described purification procedures is under reduced pressure removed and is used solvent and remaining monomer by ordinary method, or carries out sedimentation and filtration, redeposition, or carries out post separation etc. target component (A) is carried out to purifying.About reaction treatment, only otherwise can target compound just be impacted and can be undertaken by any treatment process.
For example, for above-mentioned (methyl) acrylic acid esters co-polymer (A), for the weight-average molecular weight (Mw) that makes wherein to contain be the ratio of the low molecular weight compositions below 100,000 lower than 5 quality %, preferably comprise and by following method, composition (A) carried out the purification procedures of purifying.
(purification procedures of composition (A))
Concrete grammar as the purification process of composition (A), first, at carbonatomss 5～10 such as the lower alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol or pentane, hexane, heptane, be in aliphatic hydrocarbon, particular methanol or hexane 100 mass parts, the ratio that the solids component of take is 1～30 mass parts left and right adds composition (A), at room temperature stir, precipitation is produced.Then, by methods such as decants, this throw out is carried out to solid-liquid separation, then utilize the aliphatic hydrocarbon of above-mentioned lower alcohol or carbonatoms 5～10 to clean.By comprising such purification procedures, can make weight-average molecular weight (Mw) in composition (A) is that the ratio of the low molecular weight compositions below 100,000 is lower than 5 quality %.And, in binder composition, contain composition (A) after purifying as host.
In binder composition of the present invention, by utilizing active free radical polymerization that the polymerization of mixtures of above-mentioned each monomer is manufactured to (methyl) acrylic acid esters co-polymer (A), therefore, can make mentioned component (A) become random copolymers.Above-mentioned random copolymers is irrelevant with the monomeric species for polymerization, all can obtain following the multipolymer of the monomer ratio (mol ratio) of participating in reaction.That is,, by utilizing active free radical polymerization that the mixture of above-mentioned each monomer is carried out to polymerization, with monomeric species, be that reactwity of monomer is irrelevant, all can obtain the composition (A) that each monomer is randomly polymerized.
Active free radical polymerization initiator shown in the general formula using in the present invention (1) can under condition as mild as a dove, carry out excellent molecular weight control and molecular weight distribution is controlled.
In the present invention, living radical multipolymer the weight-average molecular weight of (methyl) acrylic acid esters co-polymer (A) can control by the addition of the active free radical polymerization initiator (Organic Tellurium Compounds) shown in reaction times (polymerization time), general formula (1).Particularly, for its weight-average molecular weight is increased, as long as reduce Organic Tellurium Compounds with respect to mixing ratio, the prolongation polymerization time of monomer.But the method will obtain the composition that weight-average molecular weight is large (A) to be needed long-time.Therefore,, in order to reduce polymerization time, can enumerate: improving polymerization temperature or adding above-mentioned azo is that polymerization starter is as the method for polymerization promotor.But, if polymerization temperature is too high or azo is that the addition of polymerization starter is too much, can make the molecular weight distribution value of composition (A) increase, therefore, the molecular weight distribution of composition (A) also need to be taken into account reaction conditions is adjusted.
Like this, can easily obtain weight-average molecular weight is 400,000～2,000,000, molecular weight distribution (Mw/Mn ratio) lower than 2.5 and weight-average molecular weight be that the ratio of the low molecular weight compositions below 100,000 is lower than (methyl) acrylic acid esters co-polymer (A) of 5 quality %.
[isocyanates linking agent (B)]
In above-mentioned binder composition, contain isocyanates linking agent (B) (below also referred to as " linking agent (B) ") as essential composition.
At this, example as isocyanates linking agent (B), can enumerate: tolylene diisocyanate, diphenylmethanediisocyanate, the aromatic polyisocyanates such as xylene diisocyanate, the aliphatic polyisocyantes such as hexamethylene diisocyanate (HDI), isophorone diisocyanate, the ester ring type polyisocyanates such as hydrogenated diphenyl methane diisocyanate etc., and their biuret body, isocyanuric acid ester body, and and ethylene glycol, propylene glycol, neopentyl glycol, TriMethylolPropane(TMP), the low molecule of castor-oil plant wet goods containing the reaction product of the compound of active hydrogen be adducts (for example, TriMethylolPropane(TMP) modification tolylene diisocyanate) etc.
In the present invention, as linking agent (B), can use separately a kind in these linking agents, also can be used in combination two or more.Wherein, from the viewpoint of adhesion durability, consider, be preferably at least one in the isocyanuric acid ester body of aliphatic polyisocyantes such as being selected from aromatic polyisocyanate and HDI.In addition, its usage quantity is according to the kind of linking agent and difference, single-phase for above-mentioned (methyl) acrylic acid esters co-polymer (A) 100 mass parts, conventionally in the scope of 0.01～20 mass parts, preferably, in the scope of 0.1～10 mass parts, in the scope particularly preferably in 0.5～5 mass parts, select.
[organo-tin compound (C)]
In above-mentioned binder composition, contain organo-tin compound (C) as essential composition.
In the binder layer being formed by above-mentioned binder composition; owing to containing the tellurium compound that derives from polymerization starter in above-mentioned binder composition; therefore, the re-separation of the crosslinked delay of binder composition and the protective membrane that contains the binder layer being formed by above-mentioned binder composition becomes problem.But can solve the problems referred to above by making to contain organo-tin compound in above-mentioned binder composition.
As this organo-tin compound (C), from the viewpoint of above-mentioned effect, to consider, preference is as the existing dibutyl tin laurate (DBTDL) as crosslinking accelerator and two sad dibutyl tins (DBTDO) etc.With respect to the tellurium metal that derives from polymerization starter contained in (methyl) acrylic acid esters co-polymer (A), the content of the organo-tin compound in this binder composition (C) is the scope at 2～20 times in mass parts.That is, the ratio of the organo-tin compound (C) in preferred adhesive composition and tellurium metal is 2:1～20:1 by quality ratio.In the situation that the ratio of the organo-tin compound in binder composition (C) with respect to the tellurium metal in binder composition by quality ratio lower than 2, cannot bring into play fully above-mentioned effect, cannot realize object of the present invention.On the other hand, if the ratio of the organo-tin compound in binder composition (C) surpasses 20 by quality ratio with respect to the tellurium metal in binder composition, compared with the content of this organic compound (C), confirm less than effect raising fully.; if the ratio of the organo-tin compound in binder composition (C) and tellurium metal is 2:1～20:1 by quality ratio; can obtain fully the effect that the re-separation of the crosslinked delay of binder composition and the protective membrane that contains the binder layer being formed by above-mentioned binder composition is suppressed, therefore preferably.The more preferably ratio by quality ratio of the organo-tin compound in binder composition (C) and tellurium metal is 2:1～15:1.
[preparation of binder composition]
Preparation method as the binder composition using in the present invention, as long as having effect of the present invention is not particularly limited, such as can, by adding above-mentioned (methyl) acrylic acid esters co-polymer (A), isocyanates linking agent (B), organo-tin compound (C) and various additives such as the antioxidant using as required, UV light absorber, static inhibitor, light diffusing agent, photostabilizer, silane coupling agent, flow agent, defoamer etc. and be uniformly mixed in solvent, preparing above-mentioned binder composition.
As above-mentioned solvent, can enumerate such as the cellosolve kind solvents such as the esters such as the ketone such as the alcohol such as the halohydrocarbon such as the aromatic hydrocarbonss such as the aliphatic hydrocarbons such as hexane, heptane, toluene, dimethylbenzene, methylene dichloride, ethylene dichloride, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone, 2 pentanone, isophorone, pimelinketone, ethyl acetate, butylacetate, ethyl cellosolve, the glycol ethers solvents such as propylene glycol monomethyl ether etc.These solvents can be used separately a kind of, also can mix use two or more.
As the solid component concentration of this binder composition, as long as above-mentioned composition is the viscosity that is suitable for coating, that is, the scope that the viscosity of the above-mentioned binder composition that contains above-mentioned solvent is 100～9000mPas, is not particularly limited.
< protective membrane >
Then, protective membrane of the present invention is described.
Protective membrane of the present invention is the protective membrane with the binder layer being formed by above-mentioned binder composition.In addition, preference is as the stacked film of the folded above-mentioned binder layer at least one side upper strata at plastic film, stacked release sheet forms on above-mentioned binder layer structure.
[plastic film]
In an embodiment of protective membrane of the present invention, plastic film is used as body material.As such plastic film, as long as having effect of the present invention is just not particularly limited, for example can enumerate: polyethylene terephthalate, polybutylene terephthalate, the polyester films such as PEN, polyethylene film, polypropylene screen, glassine paper, secondary cellulose acetate film, tri cellulose acetate membrane, cellulose acetate butyrate film, polychloroethylene film, polyvinylidene chlorida film, polyvinyl alcohol film, vinyl-vinyl acetate copolymer film, Polystyrene Film, polycarbonate membrane, polymethylpentene film, polysulfone membrane, polyether-ether-ketone film, poly (ether sulfone) film, polyetherimde films, polyimide film, fluororesin film, polyamide membrane, acrylic resin film, norbornene resin film, cycloolefin resin film etc.It should be noted that, by protective membrane for the optical applications in the situation that, sometimes under the state of adherend, carry out Inspection fitting in, or use as follows: person's hobby is directly observed from it under the state of laminating protective membrane as required.Therefore,, as plastic film, be preferably overlay.
As long as the thickness of these plastic films has effect of the present invention, be not particularly limited, can suitablely select, be generally 10～250 μ m, preferably in the scope of 30～200 μ m.In addition, in order to improve this plastic film and the adaptation that is arranged at the layer on its surface, can pass through as required oxidation style, concavo-convexization method etc. single or double is implemented to surface treatment.As above-mentioned oxidation style, can enumerate such as Corona discharge Treatment, Cement Composite Treated by Plasma, chromic acid and process (wet type), flame treating, hot blast processing, ozone/uviolizing processing etc., in addition, as concavo-convexization method, can enumerate such as sand-blast, solvent treatment method etc.These surface preparations can be according to the suitable selection of the kind of plastic film, but conventionally, from the viewpoint of effect and operability etc., preferably uses Corona discharge Treatment method.In addition, also can use single or double is implemented to the plastic film that Cement Composite Treated by Plasma forms.
[binder layer]
In an embodiment of protective membrane of the present invention, at least binder layer of one side that is laminated in above-mentioned plastic film can obtain by the binder composition of the invention described above is directly coated on plastic film and is dried.In addition; further stacked release sheet thereon; also can on the demoulding treated side of release sheet, be coated with above-mentioned binder composition and be dried and form binder layer, the binder layer by this with release sheet is fitted in the one side of plastic film and forms protective membrane.
; in an embodiment of protective membrane of the present invention; what above-mentioned binder layer preferably contained mentioned component (A) and above-mentioned isocyanates linking agent (B) reacts cured article (D), and above-mentioned reaction cured article (D) preferably contains above-mentioned organo-tin compound (C) and tellurium metal.That is, above-mentioned binder layer is preferably containing responding cured article (D), organo-tin compound (C) and tellurium metal.The composition that comes from the above-mentioned Organic Tellurium Compounds that the polymerization starter as mentioned component (A) adds in binder layer during contained tellurium metal.
As the binder composition that forms above-mentioned binder layer is coated on to the method on plastic film, can make with the following method: by known method, such as blade coating (knife coat) method, rolling method, excellent painting method, scraper plate coating (blade coat) method, mould, be coated with method, intaglio plate coating method etc. and be coated with, be dried, and make it reach the method for specific thickness.
The thickness of binder layer is generally 2～30 μ m left and right, is preferably 5～25 μ m.
As above-mentioned release sheet, can enumerate: in paper such as glassine paper, enamelled paper, laminated paper and various plastics masking, be coated with release sheet that the releasing agents such as silicone resin form etc.As plastics masking, can suitably use the film of enumerating in above-mentioned plastic film.The thickness of this release sheet is not particularly limited, and is generally 10～100 μ m left and right.
Protective membrane of the present invention can form by stacked common release sheet on the face that exposes face side, do not join with plastic sheet of binder layer, also can not use in addition release sheet, on the face contrary with binder layer lamination surface of above-mentioned plastic film, release layer is set and take mode that the surface of exposing face side and above-mentioned release layer of above-mentioned binder layer joins be wound as web-like or stacked be stacked the forming of heap.
[coating]
In protective membrane of the present invention, can there is in the another side setting of the not laminating adhesive layer of plastic film the coating of antistatic property and/or antifouling property.
The another side being dried that the coating with antistatic property can be coated on by conductive material being dispersed in to the coating liquid forming in thermoplastic resin matrix for example the not laminating adhesive layer of plastic film forms.
On the other hand, the coating that has an antifouling property can form by the coating liquid that contains fluorine-type resin being coated on to the another side being dried of the not laminating adhesive layer of plastic film conventionally.
As the coating process of above-mentioned various coating liquids, can use such as excellent painting method, blade coating (knife coat) method, rolling method, scraper plate coating (blade coat) method, mould and be coated with method, intaglio plate coating method etc.
The thickness of the coating with conductivity as above forming is generally 0.05～1 μ m left and right, is preferably 0.3～0.7 μ m, and the thickness with the coating of antifouling property is generally 1～10nm left and right, is preferably 3～8nm.
[embodiment]
Then, the present invention is described in more detail, but the present invention is not subject to any restriction of these examples in conjunction with the embodiments.
It should be noted that, for the acrylate copolymer obtaining in each example, utilize gel permeation chromatography (GPC) method to obtain weight-average molecular weight (Mw), number-average molecular weight (Mn) that polystyrene standard converts, and by following method, to have obtained weight-average molecular weight be the content of the low molecular weight compositions below 100,000.
<GPC method >
Determinator: the high speed GPC device " HLC-8120GPC " that Cao Dong company manufactures is upper, by high speed post " TSK gurd column H xL-H ", " TSK Gel GMH xL", " TSK Gel G2000H xL" (above by Dong Cao company manufacture) be linked in sequence and measure according to this.
Column temperature: 40 ℃, liquor charging speed: 1.0mL/ divide, detector: differential refractometer
In addition, for the protective membrane obtaining in each example, by following method, obtain the peeling force of the bounding force of polymethylmethacrylate (PMMA), release sheet (SP) and residual particles amount (numbers of unremovable particle test).
(1) bounding force to PMMA
In the protective membrane obtaining, cut out wide 25mm, long 100mm from example below, peel off release sheet as test film, and using PMMA plate [Mitsubishi Rayon company system, " ACRYLITE L001 "] as test board.
In addition, by after test film and test board laminating, in 23 ℃, the environment of relative humidity 50%, place 24 hours, then relative humidity is being held in 50% further to following sample 1), sample 2) or sample 3) test film and test board separately, with N/25mm, measured bounding force.Wherein, sample 1): at 23 ℃, placed the sample of a week; Sample 2): at 23 ℃, placed the sample of month; Sample 3): at 40 ℃, placed the sample of two weeks.
Except above-mentioned condition, according to JIS Z0237:2009, use tensile testing machine [ORIENTEC company system, " Tensilon "], at peeling rate 300mm/, divide, measured bounding force under the condition of 180 ° of peel angle.
(2) peeling force of release sheet (SP)
Protective membrane for following example; cut out the sample of wide 50mm, long 150mm, use that tensile testing machine [ORIENTEC company system, " Tensilon "] divides at peeling rate 300mm/, the SP peeling force of having placed a week or placed each sample determination after two weeks under the condition of 180 ° of peel angle in to the environment in relative humidity 50% at 23 ℃ at 40 ℃.
(3) numbers of unremovable particle test
In dust free chamber, at room temperature by 5kg (49N) rubber rollers is made a round trip, the protective membrane obtaining in embodiment or comparative example is fitted on the minute surface of 4 inches of silicon chips, after placing 60 minutes, peel off.By laser surface test set [electronic engineering company of Hitachi system], measure retained foreign body number more than particle diameter 0.27 μ m on wafer now.
Synthesis example 1: Organic Tellurium Compounds (2-methyl-2-normal-butyl telluro-ethyl propionate) synthetic
Metallic tellurium [Aldrich company system, ProductName " Tellurium (40mesh) "] 6.38g (50mmol) is suspended in tetrahydrofuran (THF) (THF) 50ml, under room temperature, slowly drips wherein n-Butyl Lithium [Aldrich company system, 1.6mol/L hexane solution] 34.4ml (55mmol).Stir this reaction soln until metallic tellurium completely dissolve.At room temperature in this reaction soln, add 2-isobutyl ethyl bromide 10.7g (55mmol), stir two hours.After reaction finishes, under reduced pressure concentrated solvent, then carries out underpressure distillation, has obtained 2-methyl-2-normal-butyl telluro-ethyl propionate 8.98g (yield 59.5%) of yellow oil.
[embodiment 1]
(1) acrylate copolymer being formed by random copolymers by active free radical polymerization manufacture (A)
As monomer, with the ratio of mass ratio 97:3, use butyl acrylate [BA, Tokyo change into company's system] and vinylformic acid 4-hydroxyl butyl ester [4HBA, Tokyo change into company and makes], by active free radical polymerization shown below, manufactured the acrylate copolymer (A) that the random copolymers by BA/4HBA forms.The proterties of this multipolymer is shown in to table 1.
< active free radical polymerization >
In the glove box through argon displacement, 2-methyl-2-normal-butyl telluro-ethyl propionate 68.5 μ the L that make in synthesis example 1 to manufacture, butyl acrylate (the same) 107g, vinylformic acid 4-hydroxyl butyl ester (the same) 3.3g and as 2 of polymerization promotor, 2'-Diisopropyl azodicarboxylate [AIBN; Aldrich company system] 4.6mg reacts 20 hours at 60 ℃.
After reaction finishes, from glove box, take out reactor, after being dissolved in ethyl acetate 500ml, the post that this polymers soln is made by activated alumina [manufacture of He Guangchun medicine industrial].Then, add toluene, make the viscosity of polymers soln reach 5000mPas (25 ℃).The solids component of the polymkeric substance obtaining is 15.0 quality %.
In addition, the weight-average molecular weight of measuring by GPC is that the ratio of the low molecular weight compositions below 100,000 is 1.95 quality %, and the weight-average molecular weight of above-mentioned (A) composition is 1,030,000, molecular weight distribution (Mw/Mn) is 2.06.
In addition, after dry above-mentioned polymers soln, carrying out ashing treatment, by ICP/MS (Inductively coupled plasma mass spectrograph), confirm, is 100ppm with respect to the residual tellurium amount of polymers soln solids component.
(2) preparation of binder composition
Using (methyl) acrylate copolymer (A) 100 mass parts (solids component) that formed by random copolymers of manufacturing in above-mentioned (1), as isocyanuric acid ester type HDI[Japanese polyurethane industrial system, trade(brand)name " CORONATE HX ", the NCO content of linking agent (B): 21.3 quality %, solids component 100%] 2.00 mass parts and DBTDL245ppm be dissolved in the methyl ethyl ketone of solvent, and having prepared solid component concentration is the binder composition of 13 quality %.
(3) making of protective membrane
Utilize doctor knife coater, the mode that the dry thickness of usining is 5 μ m is coated on not carrying out on antistatic/antifouling treated side as the thickness 38 μ m of plastic film the antifouling polyethylene terephthalate film of static resistance [Toray company system, trade(brand)name " PET38SLD52 "] by the binder composition obtaining in above-mentioned (2), then heat drying 1 minute at 90 ℃, forms binder layer.
Then; that on the demoulding treated side of the release sheet [Lintec company system, trade(brand)name " SP-PET381031 "] of thickness 38 μ m, fits binder layer obtained above exposes face side; the protective membrane that making consists of plastic film/binder layer/release sheet, has measured each characteristic to this protective membrane.The results are shown in table 2.
[embodiment 2]
In the binder composition of embodiment 1, by the quantitative change of DBTDL 490ppm more, in addition, by operation similarly to Example 1, prepared binder composition, further made protective membrane.This protective membrane has been measured to each characteristic.The results are shown in table 2.
[embodiment 3]
In the binder composition of embodiment 1, by the quantitative change of DBTDL 979ppm more, in addition, by the operation identical with embodiment 1, prepared binder composition, further made protective membrane.This protective membrane has been measured to each characteristic.The results are shown in table 2.
[comparative example 1～4]
In the binder composition of embodiment 1, by the amount of DBTDL respectively as shown in table 1 change, in addition, by the operation identical with embodiment 1, prepared each binder composition, further made each protective membrane.This protective membrane has been measured to each characteristic.The results are shown in table 2.
[comparative example 5]
(1) by radical polymerization, manufacture acrylate copolymer
As monomer, with the ratio of mass ratio 97:3, use butyl acrylate (the same) and vinylformic acid 4-hydroxyl butyl ester (the same), by radical polymerization shown below, manufactured the acrylic acid esters co-polymer of BA/4HBA.The proterties of this multipolymer is shown in to table 1.
< radical polymerization >
To having in the reaction unit of stirrer, thermometer, reflux exchanger and nitrogen ingress pipe, enclose nitrogen, then add ethyl acetate 90 mass parts, butyl acrylate 75 mass parts, vinylformic acid 4-hydroxyl butyl ester 2.3 mass parts and as 2 of polymerization starter, 2'-Diisopropyl azodicarboxylate (AIBN) 0.2 mass parts is reacted 7 hours while stir under the reflux temperature of ethyl acetate.After reaction finishes, add toluene 95 mass parts and be cooled to room temperature.Then, obtain the acrylate copolymer that solids component is 13 quality %.
Then, by the operation identical with embodiment 1, prepare binder composition, further made protective membrane.Each characteristic of this protective membrane is shown in to table 2.
Figure BDA00003597200500211
[notes]
(1) the Te content in acrylic acid esters co-polymer (A) is measured by following method.
Measure machine: ICP/MS
After dry polymer solution, carry out ashing treatment, carried out utilizing the analysis of ICP/MS.
In addition, the abbreviation in table 1,2 is as described below.
(2) phr: with respect to the mass parts of host 100 mass parts
(3) DBTDL: dibutyl tin laurate
(4) BA: butyl acrylate
(5) 4HBA: vinylformic acid 4-hydroxyl butyl ester
(6) CORONATE HX: Japanese polyurethane industrial system, trade(brand)name, isocyanuric acid ester type HDI, NCO content: 23.1 quality %, solids component: 100%
(7) LRP: active free radical polymerization
(8) FRP: radical polymerization
[table 2]
Figure BDA00003597200500221
[notes] 1W: one week, 2W: two weeks, 1M: one month
As shown in Table 2, the bounding force of the protective membrane of embodiment is compared with the bounding force of the protective membrane of comparative example, through time the bounding force that causes reduction little.In addition, about the peeling force to release sheet, compare with the protective membrane of embodiment, the protective membrane of comparative example through time become large, re-separation increases the weight of.
In numbers of unremovable particle test; in the situation that by utilize active free radical polymerization embodiment 1～3 protective membrane and utilize the protective membrane of the comparative example 5 of radical polymerization to be compared; it is extremely many that the protective membrane of comparative example 5 tests by numbers of unremovable particle the number confirming, and is 7800.From these results, it is few that the residue thing of protective membrane of the present invention on adherend adheres to, and can prevent protective membrane because of through time the re-separation that causes.
Industrial applicibility
Protective membrane of the present invention has binder layer; the residual monomer and the low molecular weight compositions that form in the binder composition of above-mentioned binder layer are few; residue thing on adherend adheres to seldom; therefore, can be suitable for the anti-glare headed by the surface protection of various image display devices, antireflection etc.

Claims (3)

1. a protective membrane, it has binder layer,
Wherein, described binder layer is formed by the binder composition that comprises (methyl) acrylic acid esters co-polymer (A), isocyanates linking agent (B) and organo-tin compound (C), described (methyl) acrylic acid esters co-polymer (A) is that the weight-average molecular weight (Mw) that obtains by active free radical polymerization is 400,000～2,000,000, molecular weight distribution (Mw/Mn) value is lower than 2.5 multipolymer
Described (methyl) acrylic acid esters co-polymer (A) also contains tellurium metal,
Described organo-tin compound (C) in described binder composition and the ratio of described tellurium metal are 2:1～20:1 by quality ratio.
2. protective membrane according to claim 1; wherein; with respect to the total mass of described (methyl) acrylic acid esters co-polymer (A), the ratio that the middle weight-average molecular weight of described (methyl) acrylic acid esters co-polymer (A) is the low molecular weight compositions below 100,000 is lower than 5 quality %.
3. protective membrane according to claim 1 and 2, it also comprises release sheet,
Described binder layer is layered at least simultaneously upper of described plastic film,
Described release sheet is layered on described binder layer.
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