CN102119349A - Optical film with adhesive and optical laminate using same - Google Patents

Optical film with adhesive and optical laminate using same Download PDF

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CN102119349A
CN102119349A CN200980131207XA CN200980131207A CN102119349A CN 102119349 A CN102119349 A CN 102119349A CN 200980131207X A CN200980131207X A CN 200980131207XA CN 200980131207 A CN200980131207 A CN 200980131207A CN 102119349 A CN102119349 A CN 102119349A
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weight
bonding agent
methyl
blooming
acryl resin
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CN102119349B (en
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竹厚流
金容演
柳廷昊
太田阳介
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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]
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed is an optical film with adhesive wherein an adhesive layer (20) formed from a composition that contains (A), (B), and (C) is provided on an optical film (10). (A) 100 parts by weight of an acrylic resin that is a copolymer of a monomer mixture that contains: (A-1) 80-96 wt% of a (meth)acrylic acid ester with formula (I) (I) (R1 is hydrogen or a methyl, and R2 is a C1-14 alkyl), (A-2) 3-15 wt% of an unsaturated monomer that has an aromatic ring and one olefinic double bond in the molecule, and (A-3) 0.1-5 wt% of an unsaturated monomer that has a polar functional group, where the weight average molecular weight (Mw) of the acrylic resin is 1,000,000 to 2,000,000 and the molecular weight distribution (Mw/Mn) is 3 to 7. (B) 0.2-8 parts by weight of an ionic compound that has ionic cations and the melting point of which is no more than 80 C. (C) 0.01-5 parts by weight of a crosslinking agent.

Description

Band bonding agent blooming and the optical laminate that uses it
Technical field
The present invention relates to a kind of blooming that is formed with adhesive phase.As the blooming of object, can enumerate for example polarization plates or polarizer as in the present invention.The invention still further relates to a kind of use and be formed with the liquid crystal display optical laminate of the blooming of this adhesive phase.
Background technology
Polarization plates is mounted in the liquid crystal indicator and is widely used, it is forming adhesive phase at the stacked transparent protective film in the two sides of polaroid, on the surface of at least one side protective film, and pastes the state circulation of stripping film on this adhesive phase.In addition, also have to be pasted with on the polarization plates of state of diaphragm stacked phase retardation film on the two sides of polaroid and to make the elliptic polarization plate, and paste the polarization plates of adhesive phase/stripping film in this phase retardation film side.And then, also can paste adhesive phase/stripping film sometimes on the surface of phase retardation film.Stick on before the liquid crystal cells, upward stripping film is peeled, stick on the liquid crystal cells via the adhesive phase that exposes from these polarization plates, elliptic polarization plate, phase retardation film etc.Owing to such polarization plates, elliptic polarization plate or phase retardation film can produce static when pasting on the liquid crystal cells in that stripping film is peeled off, wish that therefore developing it prevents countermeasure.
As one of its countermeasure; in Japanese kokai publication hei 6-313807 communique (patent documentation 1), proposed a kind of at polarizer membrane surperficial stacked diaphragm and be provided with the polarization plates of adhesive phase on the surface of diaphragm, this polarization plates uses the composition that comprises the ionic conductivity composition that is made of electrolytic salt and organopolysiloxane and acrylic acid series copolymer as bonding agent.By using this bonding agent, shown antistatic behaviour, but its performance may not be abundant, and bonding persistence can not be said so fully.
On the other hand, in Japanese Unexamined Patent Application Publication 2004-536940 communique (patent documentation 2), disclose, in pressure-sensitive adhesive (bonding agent), cooperated the antistatic agent of organic salt, and given antistatic behaviour this bonding agent.In addition, having put down in writing in TOHKEMY 2004-114665 communique (patent documentation 3), is that the salt that 4～20 quaternary ammonium cation and the negative ion that contains fluorine atom form is given antistatic behaviour by comprising in tackifier etc. by total carbon number.And then, in TOHKEMY 2006-307238 communique (patent documentation 4), put down in writing, make contain in the bonding agent in room temperature (25 ℃) down antistatic to obtain for the ionic liquid of liquid.But, when the polarization plates that is coated with bonding agent is placed for a long time, because of through the time change antistatic behaviour variation sometimes.The circulation of general polarization plates and holding time are 6 months from making beginning the longest, so will keep antistatic property in requiring during client's use.
In addition, aforesaid band bonding agent blooming sticks on its adhesive phase side and makes liquid crystal indicator on the liquid crystal cells, but place under high temperature or the hot and humid condition or heating and when cooling repeatedly with this state, the change in size that can follow blooming produces foaming or heaves or peel off etc. in generation between blooming and adhesive phase or between adhesive phase and the liquid crystal cells glass at adhesive phase, therefore, require this undesirable condition does not take place and permanance is good.And then, when exposing at high temperature, act on the skewness of the residual stress of blooming, stress is concentrated in the peripheral part of blooming, the result, and white phenomenon or color spot are leaked in being called as that the generation peripheral part bleaches when black the demonstration, therefore, also require to suppress the white or color spot of this leakage.And then, in addition, when on liquid crystal cells, pasting band bonding agent blooming, prepare when incomplete, in case its blooming is peeled off, then to paste new film again, require when such peeling off adhesive phase to peel off together along with blooming and residual adhesive on glass and do not produce fuzzy etc. so-called re-workability not in the unit.
In TOHKEMY 2007-138056 communique (patent documentation 5), put down in writing, make alkyl acrylate and contain the aromatic rings monomer copolymerization, make the molecular weight distribution of ratio (Mw/Mn) expression of the weight-average molecular weight (Mw) of the resin that obtains and number-average molecular weight (Mn) extend to 10～50, thereby suppress the method for light leak.By using such bonding agent, can reduce light leak, but can not say so fully, and, because molecular weight distribution is wide, under hot conditions, foam sometimes.
The look-ahead technique document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 6-313807 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2004-536940 communique
Patent documentation 3: TOHKEMY 2004-114665 communique
Patent documentation 4: TOHKEMY 2006-307238 communique
Patent documentation 5: TOHKEMY 2007-138056 communique
The summary of invention
The problem that invention will solve
Problem of the present invention is, provide a kind of when giving high antistatic behaviour its antistatic behaviour do not change during The book of Changes, even maximize, leak the white also excellent bonding agent (Japanese: Ceng band bonding agent blooming sticker) that is provided with on the blooming surface that suppresses.The inventor etc. have carried out wholwe-hearted research in order to solve above-mentioned problem, found that, following composition is set as adhesive phase by surface at blooming, can obtain leak the band bonding agent blooming of preventing property, antistatic behaviour and excellent in te pins of durability in vain, thereby finished the present invention, described composition is principal ingredient with the acrylate, cooperates the acryl resin comprise from the structural unit of the unsaturated monomer that has aromatic rings in the molecule, and specific ionic compound.
The means that are used to deal with problems
Promptly, band bonding agent blooming of the present invention is characterised in that, one side at least at blooming forms adhesive phase, to have organic cation and fusing point be that the ionic compound below 80 ℃ and the adhesive composition of 0.01～5 weight portion (C) crosslinking chemical form to this adhesive phase by containing 100 weight portions (A) acryl resin, 0.2～8 weight portion (B), this adhesive phase has the gel fraction of 70～99 weight %
Described (A) acryl resin is by comprising the multipolymer that unsaturated monomer that has the two keys of an alkene and at least one aromatic rings in 80～96 weight % (A-1) (methyl) acrylate, 3～15 weight % (A-2) molecules and the monomer mixture that 0.1～5 weight % (A-3) has the unsaturated monomer of polar functional group obtain, and weight-average molecular weight (Mw) is 1,000,000～2,000,000, the molecular weight distribution shown in the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 3～7 acryl resin;
Described (A-1) (methyl) acrylate is (methyl) acrylate shown in the following formula (I),
[changing 1]
Figure BPA00001309995900031
(in the formula, R 1Expression hydrogen atom or methyl, R 2The alkyl of the carbon number 1～14 that expression can be replaced by the alkoxy of carbon number 1～10).
In addition, according to the present invention, also provide a kind of described band bonding agent blooming to be layered in the optical laminate that glass substrate forms with its adhesive phase side.
The effect of invention
Among the present invention, as the adhesive composition that is used to form adhesive phase, be combined with the unsaturated monomer (A-2) that in molecule, has the two keys of 1 alkene and at least one aromatic rings acryl resin (A) by using as constituent, and has organic cation and fusing point is the composition of the ionic compound (B) below 80 ℃, can prevent by the inhomogeneous optical defect that causes of stress distribution, therefore, can suppress to leak white, effectively suppress the charged of optics simultaneously, even, also can keep the antistatic property at initial stage from making the long-time keeping of beginning.
In addition, band bonding agent blooming of the present invention is after in a single day being layered in it on glass substrate, having under any ill-considered situation, with this blooming with bonding agent when glass substrate is peeled off, also seldom produce cull or fuzzy on the surface of the glass substrate after peeling off, can be used as glass substrate, re-workability excellence once more.
And then, band bonding agent blooming of the present invention is that 3～7 acryl resin (A) is as the adhesive composition that is used to form adhesive phase by using molecular weight distribution (Mw/Mn), leakage in the time of can preventing to form optical laminate effectively is white, simultaneously, under hot conditions, also can prevent unfavorable conditions such as foaming.And then, in addition, be set at the scope of 70～99 weight % by gel fraction with adhesive phase, the permanance of adhesive phase can be improved, the appearance change when will carry out test such as heat-resisting, moisture-proof is warm, heat shock resistance can be suppressed with bonding agent blooming the state on the glass substrate of liquid crystal cells of sticking on.
This band bonding agent blooming can provide the liquid crystal display optical laminate for example by on the glass substrate that is layered in liquid crystal cells.This optical laminate its adhesive phase under wet heat condition absorbs and relaxes the stress that the change in size by blooming and glass substrate causes, therefore, can alleviate local stress concentration, can suppress heaving or peel off etc. with respect to the adhesive phase of glass substrate.
Description of drawings
Fig. 1 is the schematic cross-section of preferred layer of example that constitutes of expression optical laminate of the present invention.
Embodiment
Below, the present invention is described in detail.Band bonding agent blooming of the present invention is formed with adhesive phase in the one side at least of blooming, the adhesive composition that forms described adhesive phase by contain (A) acryl resin, (B) have organic cation and fusing point be below 80 ℃ ionic compound, and (C) composition of crosslinking chemical form.At first, each composition that constitutes adhesive composition is described.
[acryl resin (A)]
In the band bonding agent blooming of the present invention, the employed acryl resin of adhesive composition (A) with from the structural unit of (methyl) acrylate shown in the above-mentioned formula (I) as major component, particularly, except that the structural unit that is somebody's turn to do from (methyl) acrylate, also comprise structural unit, from having with free carboxy from the unsaturated monomer that has the two keys of 1 alkene and at least 1 aromatic rings in the molecule, hydroxyl, amino, epoxide ring is the monomer of the heterocyclic radical isopolarity functional group of representative, the structural unit that preferably has (methyl) acrylic acid series compound of polar functional group.At this, (methyl) acrylic acid is meant and can be in the acrylic or methacrylic acid any that " (methyl) " when in addition, being called (methyl) acrylate etc. also has the identical meaning.
In described formula (I) as the primary structure unit of acryl resin (A), R 1Be hydrogen atom or methyl, R 2Alkyl for carbon number 1～14.R 2Hydrogen atom in each group of shown alkyl can be replaced by the alkoxy of carbon number 1～10.
In (methyl) acrylate (A-1) shown in the formula (I), as R 2Be (methyl) acrylate of non-substituted alkyl, specifically can illustration: the straight chain shape alkyl acrylate of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid n-octyl, lauryl acrylate and so on; The branching shape alkyl acrylate of isobutyl acrylate, 2-EHA, Isooctyl acrylate monomer and so on; The straight chain shape alkyl methacrylate of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, n octyl methacrylate, lauryl methacrylate and so on; The branching shape alkyl methacrylate of isobutyl methacrylate, methacrylic acid 2-Octyl Nitrite, EHMA and so on etc.
Wherein, preferred n-butyl acrylate particularly, in all monomers that constitute acryl resin (A), is more than the 50 weight % with n-butyl acrylate preferably and the mode that satisfies the above-mentioned regulation relevant with (methyl) acrylate (A-1) is used.
As R 2During the alkyl that replaces for alkoxy, R 2(methyl) acrylate of formula during for alkoxyalkyl (I) expression specifically can illustration: acrylic acid 2-methoxyl ethyl ester, acrylic acid ethoxy methyl esters, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid ethoxy methyl esters etc.
These (methyl) acrylate can be distinguished separately and to use, and also can use the different multiple copolymerization of carrying out.
The unsaturated monomer (A-2) that has the two keys of 1 alkene and at least one aromatic rings in the molecule preferably has (methyl) acryloyl group as the group that contains the two keys of alkene.As its example, can enumerate: (methyl) benzyl acrylate, neopentyl glycol benzoic ether (methyl) acrylate etc., the unsaturated monomer of preferred especially following formula (II) expression.
[changing 2]
Figure BPA00001309995900061
In the formula, R 3Expression hydrogen atom or methyl, n is 1～8 integer, R 4Expression hydrogen atom, alkyl, aralkyl or aryl.R 4During for alkyl, its carbon number can be about 1～9, and same, during for aralkyl, its carbon number can be about 7～11, and when perhaps being aryl, its carbon number can be about 6～10.
As the alkyl of carbon number 1～9, can enumerate methyl, butyl, nonyl etc., as the aralkyl of carbon number 6～11, can enumerate benzyl, phenethyl, menaphthyl etc., as the aryl of carbon number 6～10, can enumerate phenyl, tolyl, naphthyl etc.
As the unsaturated monomer of concrete formula (II), can enumerate: (methyl) acrylate of 2-phenoxy group ethyl (methyl) acrylate, 2-(2-phenoxy group ethoxy) ethyl (methyl) acrylate, oxirane modification nonyl phenol, 2-(adjacent phenyl phenoxy group) ethyl (methyl) acrylate etc.These unsaturated monomers that have the two keys of 1 alkene and at least one aromatic rings in molecule can be distinguished separately and use, and also can be used in combination different multiple.
Wherein, preferably use 2-phenoxy group ethyl (methyl) acrylate or 2-(adjacent phenyl phenoxy group) ethyl (methyl) acrylate to contain one of aromatic rings unsaturated monomer (A-2) as what constitute acryl resin (A).
As the example of the unsaturated monomer with polar functional group (A-3), can enumerate: the unsaturated monomer with free carboxy of acrylic acid, methacrylic acid, β-propyloic acrylic ester and so on; The unsaturated monomer with hydroxyl of (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-or 3-chloro-2-hydroxy propyl ester, diethylene glycol list (methyl) acrylate and so on; Acryloyl morpholine, caprolactam, N-vinyl-2-Pyrrolidone, tetrahydrofurfuryl (methyl) acrylate, caprolactone modification tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexyl methyl (methyl) acrylate, (methyl) glycidyl acrylate, 2, the unsaturated monomer with heterocyclic radical of 5-dihydrofuran and so on; N, the unsaturated monomer with amino different of N-dimethyl aminoethyl (methyl) acrylate and so on etc. with heterocycle.These unsaturated monomers with polar functional group can be distinguished separately and to use, and also can use different multiple.
Wherein, the polar functional group of unsaturated monomer (A-3) is preferably free carboxy, hydroxyl, amino or epoxide ring.The unsaturated monomer that especially preferably will have hydroxyl is as one of unsaturated monomer that contains polar functional group (A-3) that constitutes acryl resin (A).In addition, except that the unsaturated monomer with hydroxyl, and the unsaturated monomer that with the unsaturated monomer with other polar functional group, for example has a free carboxy also is effective.
The content of (methyl) acrylate (A-1) in acryl resin (A) of above-mentioned formula (I) expression is made as 80～96 weight %, be preferably more than the 82 weight %, more preferably more than the 85 weight %, be preferably in addition below the 94 weight %, more preferably below the 92 weight %.The content of unsaturated monomer (A-2) in acryl resin (A) that has the two keys of 1 alkene and at least one aromatic rings in the molecule is made as 3～15 weight %, be preferably more than the 5 weight %, more preferably more than the 5.5 weight %, be preferably especially more than the 7 weight %, be preferably in addition below the 12 weight %, more preferably below the 9.9 weight %, be preferably especially below the 9.5 weight %, further be preferably below the 9 weight %.The content of unsaturated monomer (A-3) in acryl resin (A) with polar functional group is made as 0.1～5 weight %, is preferably more than the 0.5 weight %, is preferably in addition below the 3 weight %.
The acryl resin that uses among the present invention (A) can also comprise from the unsaturated monomer (A-2) that has the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1) of the above-mentioned formula (I) of above explanation expression, the molecule and have the structural unit of unsaturated monomer (A-3) monomer in addition of polar functional group.As their example, can enumerate: from the structural unit of (methyl) acrylate that has the ester ring type structure in the molecule, from the structural unit of styrenic monomers, from the structural unit of ethene base system monomer, from structural unit of the monomer that has a plurality of (methyl) acryloyl group in the molecule etc.
So-called ester ring type structure is meant that carbon number is generally more than 5, is preferably the naphthenic hydrocarbon structure about 5～7.Concrete example as acrylate with ester ring type structure, can enumerate: isobornyl acrylate, cyclohexyl acrylate, acrylic acid two ring pentyl esters, acrylic acid cyclo-dodecyl ester, acrylic acid methyl cyclohexane ester, acrylic acid 3-methyl cyclohexanol ester, acrylic acid tert-butyl group cyclohexyl, α-ethoxy-c olefin(e) acid cyclohexyl, acrylic acid cyclohexyl phenyl ester etc., as the concrete example of methacrylate, can enumerate: isobornyl methacrylate with ester ring type structure, cyclohexyl methacrylate, methacrylic acid two ring pentyl esters, methacrylic acid cyclo-dodecyl ester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid tert-butyl group cyclohexyl, methacrylic acid cyclohexyl phenyl ester etc.
Example as styrenic monomers, except that styrene, can enumerate: the ring-alkylated styrenes of methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group styrene and so on; The halogenated styrenes of fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethene and so on; And nitrostyrolene, acetylbenzene ethene, methoxy styrene, divinylbenzene etc.
As the example of ethene base system monomer, can enumerate: the fatty acid vinyl ester of vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate and so on; The ethylene halide of vinyl chloride or bromine ethene and so on; The inclined to one side ethylene halide of vinylidene chloride and so on; The nitrogenous aromatic vinyl of vinylpyridine, vinyl pyrrolidone, vinylcarbazole and so on; The conjugate diene monomer of butadiene, isoprene, chlorbutadiene and so on; And vinyl cyanide, methacrylonitrile etc.
Example as the monomer that has a plurality of (methyl) acryloyl group in the molecule, can enumerate: 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1 has the monomer of 2 (methyl) acryloyl groups in the molecule of 9-nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate and so on; Has the monomer of 3 (methyl) acryloyl groups etc. in the molecule of trimethylolpropane tris (methyl) acrylate and so on.
Unsaturated monomer (A-3) monomer in addition that has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1) of above-mentioned formula (I) expression, the molecule and have a polar functional group can be distinguished separately and uses, or also can make up more than 2 kinds and use.Contain with respect to nonvolatile component 100 weight portions of acryl resin (A) ratio from the structural unit of above-mentioned (A-1)～(A-3) monomer in addition with common 0～20 weight portion, preferred 0～10 weight portion.
The effective constituent of bonding agent can comprise the acryl resin of structural unit that containing more than 2 kinds has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1) from aforesaid formula (I) expression, the molecule and have the unsaturated monomer (A-3) of polar functional group.And then, in the aforesaid propylene acid resin, can also mix the acryl resin different, concrete example as for having from the structural unit of (methyl) acrylate of formula (I) and not containing the acryl resin etc. of polar functional group with it.Comprise the acryl resin of structural unit that has the unsaturated monomer (A-2) of the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1) from formula (I) expression, the molecule and have a unsaturated monomer (A-3) of polar functional group and preferably be made as more than the 80 weight %, more preferably be made as more than the 90 weight % with respect to whole acryl resins.
By the unsaturated monomer (A-2) that has the two keys of 1 alkene and at least one aromatic rings in (methyl) acrylate (A-1) that comprises formula (I) expression, the molecule and to have multipolymer that the monomer mixture of the unsaturated monomer (A-3) of polar functional group obtains be that acryl resin (A) adopts weight-average molecular weight (Mw) that the polystyrene standard measured by gel permeation chromatography (GPC) the converts acryl resin in 1,000,000～2,000,000 scope.The weight-average molecular weight that polystyrene standard converts is 1,000,000 when above, and hot and humid tackiness down increases, and the possibility of heaving, peeling off between glass substrate and adhesive phase has the tendency of reduction, and re-workability has the tendency of raising, so preferably.In addition, this weight-average molecular weight is 2,000,000 when following, even sticking on the size of the blooming on the described adhesive phase changes, adhesive phase is not followed its change in size yet and is changed, therefore, do not have difference between the brightness of the edge part of liquid crystal cells and the brightness of central part, have and suppress to leak tendency white, color spot, therefore preferred.The scope of molecular weight distribution about 3～7 of ratio (Mw/Mn) expression of weight-average molecular weight (Mw) and number-average molecular weight (Mn).
In addition, for exhibit adhesiveness, aforesaid propylene acid resin (A) preferably its glass transition temperature-10～-60 ℃ scope.The glass transition temperature of resin can utilize differential scanning calorimeter to measure usually.
The acryl resin (A) that constitutes adhesive phase for example can utilize known the whole bag of tricks such as solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization to make.In the manufacturing of this acryl resin, use polymerization initiator usually.Total 100 weight portions of the whole monomers that use in the manufacturing of polymerization initiator with respect to acryl resin are about 0.001～5 weight portion.
As polymerization initiator, use thermal polymerization, Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, for example can enumerate: 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc.As thermal polymerization, for example can enumerate: 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (cyclohexane-1-nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl valeronitrile), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo based compound of 2 '-azo two (2-hydroxymethyl propionitrile) and so on; Lauroyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, tert butyl peroxy benzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxy dicarbonate, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide pivalate, peroxidating (3,5,5-trimethyl acetyl base) and so on organic peroxide; The inorganic peroxide of potassium persulfate, ammonium persulfate, hydrogen peroxide and so on etc.Also can be used as polymerization initiator in addition, and with redox series initiators of superoxide and reductive agent etc.
As the manufacture method of acryl resin, the solution polymerization process in the method shown in preferred above.
When the concrete example of enumerating solution polymerization process describes, can enumerate following method: desirable monomer and organic solvent are mixed, in nitrogen atmosphere, add thermal polymerization, about 40～90 ℃, preferred about 60～80 ℃ stir method about 3～10 hours etc.In addition, in order to control reaction, monomer, thermal polymerization can be added to continuously or off and in the polymerization or and add with the state that is dissolved in organic solvent.At this,, for example can use: toluene, dimethylbenzene and so on aromatic hydrocarbon based as organic solvent; The ester class of ethyl acetate, butyl acetate and so on; The aliphatics alcohols of propyl alcohol, isopropyl alcohol and so on; The ketone of acetone, methyl ethyl ketone, methyl isobutyl ketone and so on etc.
[ionic compound (B)]
Among the present invention, on the basis of above-described acryl resin (A), the use fusing point is the ionic compound (B) below 80 ℃.This ionic compound (B) has organic cation.
The organic cation that the cation constituent that constitutes ionic compound (B) is the ionic compound below 80 ℃ for satisfied formation fusing point gets final product, and is not particularly limited in addition.For example can enumerate: glyoxaline cation, pyridylium, ammonium cation, sulfonium cation, phosphonium cation etc., when being used for the adhesive phase of blooming, be difficult for charged viewpoint when thereon stripping film is peeled off and consider preferred pyridylium, glyoxaline cation from being provided with.The molecular weight of ionic compound (B) is not particularly limited, and for example is preferably molecular weight below 700, more preferably below 500.
On the other hand, in ionic compound (B), the anion component that becomes the counter ion counterionsl gegenions of above-mentioned cation constituent is that ionic compound below 80 ℃ just is not particularly limited as long as satisfy to form fusing point, can be inorganic anion, also organic anion can be, for example following ion can be enumerated.
Cl anion (Cl -),
Bromine anions (Br -),
Iodine negative ion (I -),
Tetrachloro aluminic acid negative ion (AlCl 4 -),
Heptachlor two aluminic acid negative ion (Al 2Cl 7 -),
Tetrafluoro boric acid negative ion (BF 4 -),
Hexafluorophosphoric acid negative ion (PF 6 -),
Perchloric acid negative ion (ClO 4 -),
Nitric acid negative ion (NO 3 -),
Acetate anion (CH 3COO -),
Trifluoracetic acid negative ion (CF 3COO -),
Loprazolam negative ion (CH 3SO 3 -),
Trifluoromethayl sulfonic acid negative ion (CF 3SO 3 -),
P-toluenesulfonic acid negative ion (p-CH 3C 6H 4SO 3 -),
Two (trifluoromethane sulfonyl group) acid imide negative ion ((CF 3SO 2) 2N -),
Three (trifluoromethane sulfonyl group) methane negative ion ((CF 3SO 2) 3C -),
Hexafluoroarsenate negative ion (AsF 6 -),
Hexafluoro-antimonic acid negative ion (SbF 6 -),
Hexafluoro niobic acid negative ion (NbF 6 -),
Hexafluoro tantalic acid negative ion (TaF 6 -),
Dimethyl phosphinic acids negative ion ((CH 3) 2POO -),
(gathering) hydrogen fluorine fluoride anion (F (HF) n -) (n is about 1～3),
Dicyanamide anion (dca) ((CN) 2N -),
Sulphur cyanogen negative ion (SCN -),
Perfluorinated butane sulfonic acid anion (C 4F 9SO 3 -),
Two (pentafluoroethane sulfonyl) acid imide negative ion ((C 2F 5SO 2) 2N -),
Perfluorobutyric acid negative ion (C 3F 7COO -),
(trifluoromethane sulfonyl group) (fluoroform carbonyl) acid imide negative ion ((CF 3SO 2) (CF 3CO) N -) etc.
Wherein, the anion component that contains fluorine atom is preferred the use from the ionic compound consideration that can obtain the antistatic property excellence, preferred especially hexafluorophosphoric acid negative ion or two (trifluoromethane sulfonyl group) acid imide negative ion.
The concrete example of the ionic compound that uses among the present invention can suitably be selected from the combination of above-mentioned cation constituent and anion component.As the compound of the combination of concrete cation constituent and anion component, can enumerate following compound.
N-hexyl pyridine hexafluorophosphate,
N-octyl group pyridine hexafluorophosphate,
N-butyl-4-picoline hexafluorophosphate,
N-octyl group-4-picoline hexafluorophosphate,
N-methyl-4-hexyl pyridine hexafluorophosphate,
N-butyl-N-crassitude hexafluorophosphate,
1-ethyl-3-methylimidazole hexafluorophosphate,
The TBuA hexafluorophosphate,
1-ethyl-3-methylimidazole tosilate,
The TBuA tosilate,
1-butyl-3-methylimidazole methane sulfonates,
(2-hydroxyethyl) trimethyl ammonium dimethyl phosphinates,
Two (trifluoromethane sulfonyl group) acid imides of (2-hydroxyethyl) trimethyl ammonium,
Two (trifluoromethane sulfonyl group) acid imides of N-methyl-4-hexyl pyridine,
Two (trifluoromethane sulfonyl group) acid imides of N-hexyl-4-picoline,
Two (trifluoromethane sulfonyl group) acid imides of tetrahexyl ammonium,
Two (trifluoromethane sulfonyl group) acid imides of tricaprylmethylammonium,
Two (trifluoromethane sulfonyl group) acid imides of tributyl-methyl phosphonium ammonium etc.
Such ionic compound (B) can use separately also can make up more than 2 kinds and use.The example of ionic compound (B) is not limited to the above compound of enumerating.
Fusing point be below 80 ℃ ionic compound (B) as mentioned above, to keep in antistatic behaviour on each rerum natura as bonding agent be effective giving the adhesive phase that formed by the composition that comprises acryl resin (A).When the fusing point of this ionic compound is too high, and the compatibility variation of acryl resin (A), therefore, preferably have the fusing point below 80 ℃, more preferably have the fusing point below 70 ℃.In addition, consider that from the viewpoint of the long-time stability of antistatic behaviour ionic compound (B) preferably has the fusing point more than 30 ℃, the fusing point that more preferably has more than 35 ℃ is favourable.Thus, normal temperature (25 ℃) down for the ionic compound of solid (B) with compare for the ionic compound of liquid at normal temperatures, can keep being combined with the antistatic property of its adhesive phase for a long time.
With respect to the nonvolatile component of aforesaid propylene acid resin (A) (from the total amount of the structural unit of above-mentioned A-1, A-2 and A-3) 100 weight portions, contain the ionic compound (B) of the ratio of 0.2～8 weight portion.With respect to nonvolatile component 100 weight portions of acryl resin (A), when containing the above ionic compound of 0.2 weight portion (B), antistatic property improves, and is therefore preferred, and in addition, its amount is 8 weight portions when following, keeps permanance easily, therefore preferably.It is above and below 3 weight portions to be preferably 0.5 weight portion with respect to the amount of the ionic compound (B) of nonvolatile component 100 weight portions of acryl resin (A).
[crosslinking chemical (C)]
In above-described acryl resin (A) and ionic compound (B), further cooperate crosslinking chemical (C), as adhesive composition.Crosslinking chemical (C) in molecule, have at least 2 can and acryl resin (A) in particularly from the compound of the crosslinked functional group of the structural unit of unsaturated monomer with polar functional group, specifically can illustration: isocyanates based compound, epoxy based compound, metal-chelate syzygy compound, aziridine based compound etc.
(for example can enumerate: toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenation of benzene dimethyl diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc. by compound NCO) in order to have at least 2 isocyanate group in molecule for the isocyanates based compound.In addition, make polyol reaction gained such as these isocyanate compounds and glycerine, trimethylolpropane adduct, and the dimer of isocyanate compound, tripolymer etc. also can be with the crosslinking chemical that acts on bonding agent.Also can mix isocyanates based compound use more than 2 kinds.
The compound of epoxy based compound in molecule, having at least 2 epoxy radicals, for example can enumerate: bisphenol A type epoxy resin, ethylene glycol bisthioglycolate glycidyl ether, polyglycol diglycidyl ether, glycerine diglycidyl ether, glycerine triglycidyl group ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane tris glycidyl ether, N, N-diglycidylaniline, N, N, N ', N '-four glycidyl group m-xylene diamine, 1, two (N, N-diglycidyl amino methyl) cyclohexanes of 3-etc.Also can be mixed with two or more the epoxy based compound.
As metal-chelate combination compound, for example can enumerate: compound of coordination diacetone or ethyl acetoacetate etc. on polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium.
The aziridine based compound is for having at least 2 compounds that are also referred to as 3 yuan of ring skeletons that are made of 1 nitrogen-atoms and 2 carbon atoms of ethylenimine in molecule; for example can enumerate: diphenyl methane-4; 4 '-two (1-aziridine formamides); Toluene-2,4-diisocyanate; 4-two (1-aziridine formamide); triethylenemelamine; the isophthaloyl base is two-1-(2-methylaziridine); three-1-aziridine phosphine oxide; hexa-methylene-1,6-two (1-aziridine formamide); trimethylolpropane-three-β-aziridine propionate; tetramethylol methane-three-β-aziridine propionate etc.
In these crosslinking chemicals, preferably use isocyanates based compound, particularly xylylene diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; Or the adduct of these isocyanate compounds and polyol reaction gained such as glycerine or trimethylolpropane; The dimer of isocyanate compound, tripolymer etc.; The potpourri of these isocyanates based compounds etc.The unsaturated monomer (A-3) that contains polar functional group is when having the polar functional group that is selected from free carboxy, hydroxyl, amino and the epoxide ring, and particularly at least a as crosslinking chemical (C) preferably used the isocyanates based compound.As preferred isocyanates based compound, can enumerate: the adduct of toluene diisocyanate, toluene diisocyanate and polyol reaction gained; The dimer of toluene diisocyanate, and the tripolymer of toluene diisocyanate; In addition, the adduct of hexamethylene diisocyanate, hexamethylene diisocyanate and polyol reaction gained; The dimer of hexamethylene diisocyanate, and the tripolymer of hexamethylene diisocyanate.
Crosslinking chemical (C) is with respect to acryl resin (A) 100 weight portions to be the ratio cooperation of 0.01～5 weight portion.The use level of crosslinking chemical (C) is about 0.1～5 weight portion with respect to acryl resin (A) 100 weight portions preferably, more preferably about 0.2～3 weight portion.With respect to the amount of acryl resin (A) 100 parts by weight of cross-linking agent (C) be 0.01 weight portion above, in particular for 0.1 weight portion when above, the permanance of adhesive phase is tended to improve, therefore preferred, in addition, be that 5 weight portions are when following, leakage leucismus when band bonding agent blooming is applied to liquid crystal indicator gets not obvious, and is therefore preferred.
[constituting other composition of bonding agent]
In the adhesive composition that is used to form adhesive phase of the present invention, in order to improve the adaptation of adhesive phase and glass substrate, preferably contain silane based compound (D), contain silane based compound (D) particularly preferably in cooperating in the crosslinking chemical acryl resin before.
As silane based compound (D), for example can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, the 3-mercaptopropyl trimethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group dimethoxy-methyl silane, 3-glycidoxy propyl group ethoxy dimethylsilane etc.Can use silane based compound (D) more than 2 kinds.
Silane based compound (D) can be the silane based compound of silicone oligomeric.When representing the silicone oligomer, can enumerate for example following compound with the form of multipolymer.
3-mercaptopropyl trimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-mercaptopropyl trimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-mercaptopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains the mercapto propyl group of 3-mercaptopropyltriethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
Thiopurine methyltransferase trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
Thiopurine methyltransferase trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
Thiopurine methyltransferase triethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains thiopurine methyltransferase of thiopurine methyltransferase triethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-methacryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains methacryloxypropyl of 3-methacryloxypropyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-acryloxy propyl trimethoxy silicane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl trimethoxy silicane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl-triethoxysilicane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl-triethoxysilicane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains the acryloxy propyl group of 3-acryloxy propyl group methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
Vinyltrimethoxy silane-tetramethoxy-silicane alkyl copolymer,
Vinyltrimethoxy silane-tetraethoxy-silicane alkyl copolymer,
Vinyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
Vinyltriethoxysilane-tetraethoxy-silicane alkyl copolymer,
Vinyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
Vinyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
Vinyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains vinyl of vinyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-TSL 8330-tetramethoxy-silicane alkyl copolymer,
3-TSL 8330-tetraethoxy-silicane alkyl copolymer,
3-aminopropyltriethoxywerene werene-tetramethoxy-silicane alkyl copolymer,
3-aminopropyltriethoxywerene werene-tetraethoxy-silicane alkyl copolymer,
3-aminopropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-aminopropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-aminopropyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains amino of 3-aminopropyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on etc.
These silane based compounds (D) in most cases are liquid.The use level of the silane based compound in the bonding agent is generally about 0.01～10 weight portion with respect to nonvolatile component 100 weight portions (use under the situation more than 2 kinds and add up to weight for it) of acryl resin (A), is preferably 0.03～1 weight portion.With respect to the amount of the silane based compound of nonvolatile component 100 weight portions of acryl resin is more than 0.01 weight portion, in particular for 0.03 weight portion when above, and the adaptation of adhesive phase and glass substrate improves, and is therefore preferred.In addition, its amount be 10 weight portions following,, have and suppress the tendency that the silane based compound oozes out from adhesive phase when following in particular for 1 weight portion, therefore preferred.
In the bonding agent of above explanation, can and then cooperate crosslinking catalyst, weather-proof stabilizing agent, tackifier, plastifier, softening agent, dyestuff, pigment, inorganic filler, acryl resin (A) resin in addition etc.In addition, in bonding agent, cooperate ultra-violet solidified compound, to form at adhesive phase that the back irradiation ultraviolet radiation makes its curing and make harder adhesive phase also be useful.Wherein, if in bonding agent, cooperate crosslinking catalyst with crosslinking chemical, then can prepare adhesive phase by the slaking of short time, between resin molding and adhesive phase, produce in the band adhesive resin film that can suppress to obtain and heave, peel off or in adhesive phase, foam, in addition, re-workability is also better sometimes.As crosslinking catalyst, for example can enumerate: the aminated compounds of hexamethylene diamine, ethylenediamine, polyethylene imine based, hexamethylene tetramine, diethylene triamine, trien, isophorone diamine, trimethylene diamines, poly-amino resins, melamine resin and so on etc.When in bonding agent, cooperating the aminated compounds as crosslinking catalyst,, be preferably isocyanate ester compound as crosslinking chemical.
Above-mentioned each composition that constitutes bonding agent forms adhesive composition being dissolved under the state of solvent, is coated on the suitable base material and makes its drying, makes adhesive phase.
[gel fraction of adhesive phase]
As the above content of being narrated among the present invention, the gel fraction that makes adhesive phase is 70～99 weight %.At this, gel fraction is based on the value that following (I)～(IV) measures.
The wire gauze that is made of SUS304 of the adhesive phase of area that (I) will about 8cm * about 8cm and about 10cm * about 10cm (with its weight as Wm) is fitted.
(II) weight of the applying thing that obtains in the weighing above-mentioned (I), with this weight as Ws, then folding 4 times and with the fixing weighing afterwards of contract Keyes (stapler) suddenly in the mode that wraps into adhesive phase, with this weight as Wb.
(III) in glass container, pack into by above-mentioned (II) with the securing silk screen of contract Keyes suddenly, add ethyl acetate 60mL dipping after, this glass container was at room temperature preserved 3 days.
(IV) silk screen is taken out from glass container, drying is 24 hours under 120 ℃, and weighing as Wa, divides rate based on the following formula calculated for gel with its weight.
Gel fraction (weight %)=[Wa-(Wb-Ws)-Wm}/(Ws-Wm)] * 100
The gel fraction that makes adhesive phase is 70～99 weight %.Its gel fraction is 70 weight % when above, and the permanance of adhesive phase improves, and is therefore preferred, and in addition, its gel fraction is 99 weight % when following, makes easily, therefore preferably.
The gel fraction of adhesive phase for example can be that the kind of acryl resin (A) and the amount of crosslinking chemical are adjusted according to the effective constituent of adhesive phase.Particularly, when making the amount increase of the unsaturated monomer with polar functional group (A-3) in the acryl resin (A) or making the amount increase of the crosslinking chemical (C) in the adhesive composition, gel fraction increases, therefore, regulating gel fraction according to the amount of unsaturated monomer with polar functional group and/or crosslinking chemical gets final product.Therefore, about unsaturated monomer (A-3) with polar functional group, from the scope of 0.1～5 weight % according to and constitute combination and the kind of crosslinking chemical and the combination of amount of other composition of acryl resin (A), select and the amount of regulating the unit of the unsaturated monomer with described polar functional group (A-3) that derives from the acryl resin (A) gets final product in the mode of above-mentioned scope with gel fraction.In addition, about the amount of crosslinking chemical (C), preferably the scope from about 0.1～5 weight portion is selected the use level of the crosslinking chemical of nonvolatile component 100 weight portions (when using more than 2 kinds is its total amount) with respect to the acryl resin (A) that constitutes adhesive phase according to the kind of acryl resin.
[band bonding agent blooming]
Band bonding agent blooming of the present invention is provided with the adhesive phase that is formed by aforesaid adhesive composition in the one side at least of blooming.Blooming used herein is the film with optical characteristics, for example can enumerate polarization plates, phase retardation film etc.
Polarization plates is meant that incident light such as relative natural light has the blooming of the function that penetrates polarized light.Have in the polarization plates: straight line polarization plates with character of rectilinearly polarized light that absorbs vibration plane and the rectilinearly polarized light that transmission has perpendicular vibration plane with certain orientation; Polarized light separation membrane with character of rectilinearly polarized light that reflects vibration plane and the rectilinearly polarized light that transmission has perpendicular vibration plane with certain orientation; Be laminated with the elliptic polarization plate of polarization plates and phase retardation film described later etc.As polarization plates, the particularly rectilinearly polarized light film preferred concrete example of (being called as polaroid or polarizer membrane sometimes), can be set forth in the polarization plates of adsorbing dichromatism pigments such as orientation iodine or dichroic dye in the polyvinyl alcohol resin film of uniaxial tension.
Phase retardation film is meant the anisotropic blooming of display optical, for example can enumerate: by being stretched as stretched film that obtains about 1.01～6 times etc. by the polymeric membrane that polyvinyl alcohol (PVA), polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfones, polyethersulfone, Kynoar/polymethylmethacrylate, liquid crystal polyester, cellulose acetate, ethylene-vinyl acetate copolymer saponated material, Polyvinylchloride etc. constitute.Wherein, the polymeric membrane that forms of preferred uniaxial tension or biaxial stretch-formed polycarbonate membrane or cyclic polyolefin mesentery.The film that is called as single shaft phase retardation film, Wide-angle phase retardation film, low light elastic modulus phase retardation film etc. is arranged, can be suitable for any.
In addition, the coating by liquid crystal compounds, orientation show optically anisotropic film or the coating by inorganic layered compounds and show optically anisotropic film and also can be used as phase retardation film.This phase retardation film has the film that is called as the temperature compensating type phase retardation film, and the film that forms of the rod shaped liquid crystal twisted-oriented of selling with the trade name of " LC film " by Shin Nihon Oil Co., Ltd, the film that forms of the rod shaped liquid crystal tilted alignment of selling with the trade name of " NH film " by Shin Nihon Oil Co., Ltd equally, the film that the discoid liquid crystal tilted alignment of being sold with the trade name of " WV film " by Fuji Photo Film Co., Ltd. forms, by the film of Sumitomo Chemical Co with the complete biaxial orienting type of the trade name sale of " VAC film ", the film of the biaxial orienting type of selling with the trade name of " new VAC film " by Sumitomo Chemical Co etc. equally.
And then the film that is pasted with diaphragm on these bloomings also can be used as blooming.As diaphragm; use transparent resin molding; as this transparent resin, for example can enumerate with Triafol T or cellulose diacetate and be the acetate fiber prime system resin of representative, be methacrylic resin, vibrin, polyolefin-based resins, polycarbonate resin, polyether-ether-ketone resin, polysulfone resin of representative etc. with the polymethylmethacrylate.Can in the resin that constitutes diaphragm, cooperate ultraviolet light absorbers such as salicylate based compound, benzophenone based compound, benzotriazole based compound, triazine based compound, cyanoacrylate based compound, nickel complex salt compounds.As diaphragm, preferably use cellulose acetate resin films such as three cellulose acetate membrane.
In the blooming of above explanation, the straight line polarization plates is used with the state that the one or both sides at the polarizer membrane that constitutes its polaroid, for example is made of polyvinyl alcohol resin are pasted with diaphragm mostly.In addition, above-mentioned elliptic polarization plate is the polarization plates that is laminated with straight line polarization plates and phase retardation film, and this polarization plates also mostly is the state that is pasted with diaphragm at the one or both sides of polarizer membrane greatly.When on this elliptic polarization plate, forming adhesive phase of the present invention, form adhesive phase in its phase retardation film side usually.
Band bonding agent blooming is preferably pasted stripping film on the surface of its adhesive phase, in protection adhesive layer surface when using.The band bonding agent blooming that is provided with stripping film like this can be made by for example following method: the above-mentioned adhesive composition of coating forms adhesive phase on stripping film, the method for further laminated optical film on the adhesive phase that obtains; The coating adhesive composition forms adhesive phase on blooming, pastes stripping film then and protect on its bonding agent face, obtains with the method for bonding agent blooming etc.Stripping film used herein for example can for the film that constitutes by various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylates as base material, the film of gained etc. is handled in the demoulding that silicone-treated and so on is implemented on the composition surface of this base material and adhesive phase.
The thickness of adhesive phase is not particularly limited, and preferably is generally below the 30 μ m, in addition, is preferably more than the 10 μ m, more preferably 15～25 μ m.The thickness of adhesive phase is that 30 μ m are when following, tackiness under hot and humid improves, between glass substrate and adhesive phase, produce the possibility of heaving or peeling off and tend to step-down, and, re-workability tends to improve, therefore preferred, in addition, its thickness is 10 μ m when above, changes even paste the size of blooming thereon, and bonding coat is also followed this change in size and changed, therefore, do not have difference between the brightness of the edge part of liquid crystal cells and the brightness of central part, the tendency that suppresses to leak white or color spot is arranged, therefore preferred.At present, the standard of thickness that is pasted on the adhesive phase of liquid crystal cells glass is generally 25 μ m, in the present invention, even be below the 20 μ m with this thickness setting, also brings into play sufficient performance as adhesive phase.
Band bonding agent blooming of the present invention is bonded in glass substrate and after forming optical laminate, exist any imappropriate and with this blooming when glass substrate is peeled off, adhesive phase is followed blooming and is stripped from, produce fuzzy or cull etc. hardly on the surface of the glass substrate that is connected with adhesive phase, therefore, paste band bonding agent blooming more again on the glass substrate after peeling off easily.That is so-called re-workability excellence.
[optical laminate]
Band bonding agent blooming of the present invention can be laminated on the glass substrate with its adhesive phase, makes optical laminate.In the time will being with that the bonding agent blooming is stacked makes optical laminate in glass substrate, for example, peel stripping film from the band bonding agent blooming that obtains as described above, the surface that the adhesive phase that will expose fits in glass substrate gets final product.At this,, for example can enumerate as glass substrate: the glass substrate of liquid crystal cells, anti-dazzle with glass, sunglasses with glass etc.Wherein, the optical laminate that stacked other band bonding agent blooming (lower polarizing plate) forms on stacked band bonding agent blooming (upper deflection board) on the glass substrate of the front face side (identification side) of liquid crystal cells, glass substrate in the rear side of liquid crystal cells can be with the panel that acts on liquid crystal indicator (liquid crystal panel), and is therefore preferred.As the material of glass substrate, for example can enumerate: soda-lime glass, glass with lower alkali content, alkali-free glass etc.
For optical laminate of the present invention, the example that several preferred layers are constituted is shown in Fig. 1 with schematic cross-section.In the example shown in Fig. 1 (A), the diaphragm 3 that will have a surface-treated layer 2 sticks on a face of straight line polarizing coating 1 with the face that is in opposition side with described surface-treated layer 2, constitutes polarization plates 5.In this embodiment, polarization plates 5 also becomes said blooming 10 among the present invention simultaneously.Straight line polarizing coating 1 be in the adhesive phase that comprises ionic compound 20 that above explanation is set on the face of opposition side with diaphragm 3, constitute band bonding agent blooming 25.And, the face that is in opposition side with polarization plates 5 of described adhesive phase 20 is sticked on the liquid crystal cells 30 as glass substrate, constitute optical laminate 40.
In the example shown in Fig. 1 (B); first diaphragm 3 that will have a surface-treated layer 2 sticks on a face of straight line polarizing coating 1 with the face that is in opposition side with described surface-treated layer 2; on the another side of straight line polarizing coating 1, paste second diaphragm 4, constitute polarization plates 5.In this embodiment, polarization plates 5 becomes said blooming 10 among the present invention simultaneously.The adhesive phase that comprises ionic compound 20 that illustrates more than the arranged outside of second diaphragm 4 that constitutes polarization plates 5 constitutes band bonding agent blooming 25.And, the face that is in opposition side with polarization plates 5 of described adhesive phase 20 is sticked on the liquid crystal cells 30 as glass substrate, constitute optical laminate 40.
In the example shown in Fig. 1 (C), the diaphragm 3 that will have a surface-treated layer 2 sticks on a face of straight line polarizing coating 1 with the face that is in opposition side with described surface-treated layer 2, constitutes polarization plates 5.Being on the face of opposition side of straight line polarizing coating 1 with diaphragm 3, paste phase retardation film 7 via interlayer adhesive 8, constitute blooming 10.The adhesive phase that comprises ionic compound 20 that illustrates more than the arranged outside of the phase retardation film 7 that constitutes blooming 10 constitutes band bonding agent blooming 25.And, the face that is in opposition side with blooming 10 of described adhesive phase 20 is sticked on the liquid crystal cells 30 as glass substrate, constitute optical laminate 40.
In addition; in the example shown in Fig. 1 (D); first diaphragm 3 that will have a surface-treated layer 2 sticks on a face of straight line polarizing coating 1 with the face that is in opposition side with described surface-treated layer 2, pastes second diaphragm 4 at the another side of straight line polarizing coating 1, constitutes polarization plates 5.Phase retardation film 7 is pasted via interlayer adhesive 8 in the outside at second diaphragm 4 that constitutes polarization plates 5, constitutes blooming 10.The adhesive phase that comprises ionic compound 20 that illustrates more than the arranged outside of the phase retardation film 7 that constitutes blooming 10 constitutes band bonding agent blooming 25.And, the face that is in opposition side with blooming 10 of described adhesive phase 20 is sticked on the liquid crystal cells 30 as glass substrate, constitute optical laminate 40.
In these examples, usually, first diaphragm 3 and second diaphragm 4 are made of three cellulose acetate membrane, in addition, also can be made of above-described various transparent resin films.In addition, the surface-treated layer that is formed at the surface of first diaphragm 3 can be hard conating, antiglare layer, anti-reflection layer, antistatic layer etc.A plurality of these layers also can be set.
As Fig. 1 (C) and the example (D), on polarization plates 5, during stacked phase retardation film 7,, then, can enumerate 1/4 wavelength plate as the preferred example of this phase retardation film 7 if be middle-size and small-size liquid crystal indicator.Under this situation, usually, with the absorption axes of polarization plates 5 with as the hysteresis of the phase retardation film 7 of 1/4 wavelength plate mutually axle show the mode that 45 degree report to the leadship after accomplishing a task greatly and be configured, but its angle is offset to a certain degree by 45 degree.On the other hand, if be large-scale liquid crystal indicator such as televisor, then phase difference compensation or the field angle with liquid crystal cells 30 is compensated for as purpose, uses the phase retardation film with various phase difference values according to the characteristic of this liquid crystal cells 30.Under this situation, usually, with the hysteresis of the absorption axes of polarization plates 5 and phase retardation film 7 mutually the mode of an approximate vertical or almost parallel be configured.When constituting phase retardation film 7, preferably use the stretched film of single shaft or twin shaft by 1/4 wavelength plate.In addition, be compensated for as purpose and when phase retardation film 7 is set with the phase difference compensation of liquid crystal cells 30 or field angle, except that single shaft or biaxially-stretched film, can also use at the film of single shaft or biaxial stretch-formed basic upper edge thickness direction orientation, coating of liquid crystalline equiphase difference manifests material and makes the fixing film of its orientation etc. be called as the film of optical compensation films as phase retardation film 7 on support membrane.
Equally, shown in Fig. 1 (C) and example (D), when pasting polarization plates 5 and phase retardation film 7 via interlayer adhesive 8, described interlayer adhesive 8 also can use the such antistatic agent of the ionic compound that is combined with above explanation, be endowed the bonding agent of antistatic behaviour, in the common expectation antistatic behaviour within reason of this part, therefore, common use does not comprise the general acrylic adhesive of antistatic agent.In addition, large-scale liquid crystal indicator as previously discussed, when the mode of the relation of axle approximate vertical or almost parallel is configured mutually with the hysteresis of the absorption axes that becomes polarization plates 5 and phase retardation film 7, polarization plates 5 and phase retardation film 7 volume to volume ground can be pasted, in the purposes that does not require releasable between the two, also can replace Fig. 1 (C) and (D) shown in interlayer adhesive 8, use in case the gluing tackifier that just engages and can not peel off securely.As such tackifier, for example can enumerate: constitute and by making aqueous solvent evaporation obtain the water system tackifier of adhesive power, being cured the ultraviolet hardening tackifier that obtains adhesive power etc. by irradiation ultraviolet radiation by aqueous solution or aqueous dispersions.
Need to prove that the material self that is formed with the adhesive phase 20 that contains ionic compound on phase retardation film 7 shown in Fig. 1 (C) reaches (D) also can circulate with himself, can be used as the band bonding agent blooming described in the present invention.The band bonding agent blooming that is formed with the adhesive phase that contains ionic compound on phase retardation film is made the optical laminate on the liquid crystal cells that its adhesive phase can be sticked on as glass substrate, can also paste polarization plates in its phase retardation film side and make other band bonding agent blooming.
Among Fig. 1 illustration supposition will be configured in the example of situation of the identification side of liquid crystal cells 30 with bonding agent blooming 25, but band bonding agent blooming of the present invention also can be configured in liquid crystal cells rear side, be the backlight side.When band bonding agent blooming of the present invention is configured in the rear side of liquid crystal cells, can replace the diaphragm with surface-treated layer 23 shown in Figure 1, adopt the diaphragm do not have surface-treated layer, all the other and Fig. 1 (A)～(D) is same formation.In addition, under this situation, also can be at the various bloomings of known configurations such as the arranged outside brightness improving film of the diaphragm that constitutes polarization plates, condensing film, diffusion barrier in the rear side of liquid crystal cells.
As described above, optical laminate of the present invention can be preferred for liquid crystal indicator.The notebook computer that the liquid crystal indicator that is formed by optical laminate of the present invention can be used to comprise notebook type for example, desk-top, PDA (Personal Digital Assistance) etc. with LCD, televisor, vehicle with display, e-dictionary, digital camera, digital camera, electronic desktop computer, clock and watch etc.
Embodiment
Below, enumerate embodiment and further specifically describe the present invention, but the present invention is not limited by these examples.In the example, expression use amount or content " part " reaches " % ", unless otherwise specified, is weight basis just.
In following example, nonvolatile component is to use the value of measuring based on the method for JIS K 5407.Particularly, the binder solution of any weight of weighing is put into glassware, will in explosion-proof baking oven, represent with the ratio of the weight of the initial relatively solution of measuring with the residual nonvolatile component weight of 115 ℃ of dryings after 2 hours.In addition, the mensuration of weight-average molecular weight is following carries out, " the GPC KF-802 " of " the TSK gel XL " of 4 eastern ソ one of series connection (strain) system, 1 Shodex (strain) system amounts to 5 as chromatographic column in the GPC device, use tetrahydrofuran as dissolution fluid, under sample solution concentration 5mg/ml, sample import volume 100 μ l, 40 ℃ of temperature, flow velocity 1ml/ minute condition, utilize standard styrene to convert and carry out.
At first, the acryl resin (A) stipulated among the present invention of the major component that becomes adhesive composition and similar with it but depart from the example of the acryl resin of regulation of the present invention has been made in expression.
[polymerization example 1]
Possess cooling tube, nitrogen ingress pipe, temperature take into account add 81.8 parts of ethyl acetates in the reaction vessel of stirring machine, as 93.6 parts of the butyl acrylates of (A-1), as 5.0 parts of the acrylic acid 2-phenoxy ethyl of (A-2), as the mixed solution of 0.4 part in 1.0 parts of the acrylic acid 2-hydroxy methacrylates of (A-3) and acrylic acid, make its oxygen-free gas with the air in the nitrogen replaceable equipment, simultaneously, with interior temperature rise to 55 ℃.Add complete soln that azoisobutyronitrile (polymerization initiator) 0.14 part be dissolved in ethyl acetate 10 part gained thereafter.Add initiating agent after 1 hour, with the concentration of the acryl resin that do not comprise monomer is that 35% mode is added on ethyl acetate in the reaction vessel with 17.3 parts/hr of interpolation speed continuously, simultaneously, be incubated 12 hours down for 54～56 ℃ in interior temperature, adding ethyl acetate at last, is that 20% mode is regulated with the concentration of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,710,000, Mw/Mn is 4.3.With it as acryl resin A.The structural unit that derives from hydroxyl unsaturated monomer among the acryl resin A and be acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 2]
More 90.6 parts of the quantitative changes of the butyl acrylate in monomer is formed, the quantitative change of acrylic acid 2-phenoxy ethyl more 8.0 parts, is operated equally with polymerization example 1, obtained the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,740,000, Mw/Mn is 4.1.With it as acryl resin B.From the hydroxyl unsaturated monomer among the acryl resin B is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 3]
More 88.6 parts of the quantitative changes of the butyl acrylate in monomer is formed, the quantitative change of acrylic acid 2-phenoxy ethyl more 10.0 parts, is operated equally with polymerization example 1, obtained the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,560,000, Mw/Mn is 4.5.With it as acryl resin C.From the hydroxyl unsaturated monomer among the acryl resin C is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 4: relatively use]
More 78.6 parts of the quantitative changes of the butyl acrylate in monomer is formed, the quantitative change of acrylic acid 2-phenoxy ethyl more 20.0 parts, is operated equally with polymerization example 1, obtained the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,370,000, Mw/Mn is 4.4.With it as acryl resin D.From the hydroxyl unsaturated monomer among the acryl resin D is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 5: relatively use]
More 58.6 parts of the quantitative changes of the butyl acrylate in monomer is formed, the quantitative change of acrylic acid 2-phenoxy ethyl more 40.0 parts, is operated equally with polymerization example 1, obtained the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,270,000, Mw/Mn is 4.4.With it as Eudragit E.From the hydroxyl unsaturated monomer in the Eudragit E is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 6: relatively use]
More 38.6 parts of the quantitative changes of the butyl acrylate in monomer is formed, the quantitative change of acrylic acid 2-phenoxy ethyl more 60.0 parts, is operated equally with polymerization example 1, obtained the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,270,000, Mw/Mn is 5.0.With it as acryl resin F.From the hydroxyl unsaturated monomer among the acryl resin F is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 7: relatively use]
The amount of the butyl acrylate in monomer is formed is made as 98.6 parts, does not use the acrylic acid 2-phenoxy ethyl, operates equally with polymerization example 1, obtains the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,470,000, Mw/Mn is 4.4.With it as acryl resin G.From the hydroxyl unsaturated monomer among the acryl resin G is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
[polymerization example 8]
More 88.4 parts of the quantitative changes of the butyl acrylate in monomer is formed, with more 10.0 parts of the quantitative changes of acrylic acid 2-phenoxy ethyl, acrylic acid quantitative change more 0.6 part, is operated equally with polymerization example 1, obtain the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,530,000, Mw/Mn is 4.8.With it as acryl resin H.From the hydroxyl unsaturated monomer among the acryl resin H is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.6%.
[polymerization example 9]
Monomer formed change to: as 78.4 parts of the butyl acrylates of (A-1) and 10.0 parts of acrylic acid 2-methoxyl ethyl esters, as 10.0 parts of the acrylic acid 2-phenoxy ethyl of (A-2), as 0.6 part in 1.0 parts of the acrylic acid 2-hydroxy methacrylates of (A-3) and acrylic acid, in addition, operate equally with polymerization example 1, obtain the ethyl acetate solution of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,540,000, Mw/Mn is 4.9.With it as acryl resin I.From the hydroxyl unsaturated monomer among the acryl resin I is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.6%.
[polymerization example 10: relatively use]
In the reaction vessel identical, add 81.8 parts of ethyl acetates with the container that uses in the polymerization example 1, as 90.6 parts of the butyl acrylates of (A-1), as 8.0 parts of the acrylic acid 2-phenoxy ethyl of (A-2), as the mixed solution of 0.4 part in 1.0 parts of the acrylic acid 2-hydroxy methacrylates of (A-3) and acrylic acid, make its oxygen-free gas with the air in the nitrogen replaceable equipment, simultaneously, with interior temperature rise to 55 ℃.Add complete soln that azoisobutyronitrile (polymerization initiator) 0.14 part be dissolved in ethyl acetate 10 part gained thereafter.Adding initiating agent after 1 hour, is that 35% mode is added on ethyl acetate in the reaction vessel continuously with 17.3 parts/hr of interpolation speed with the concentration of the acryl resin that do not comprise monomer, simultaneously, and in the insulation 4 hours down of 54～56 ℃ of interior temperature.Thereafter, add the complete soln that azoisobutyronitrile (polymerization initiator) 0.2 part is dissolved in gained in 10 parts of the ethyl acetates, insulation is 8 hours under uniform temp, adds ethyl acetate at last, is that 20% mode is regulated with the concentration of acryl resin.The weight-average molecular weight Mw that utilizes the polystyrene conversion that GPC measures of the acryl resin that obtains is 1,070,000, Mw/Mn is 8.2.With it as acryl resin J.From the hydroxyl unsaturated monomer among the acryl resin J is that the structural unit of acrylic acid 2-hydroxy methacrylate is 1%, and in addition, coming self-contained carboxyl unsaturated monomer is that acrylic acid structural unit is 0.4%.
The complete list of the monomer composition of polymerization example 1～10, weight-average molecular weight, Mw/Mn is shown in table 1.In the table, BA is meant butyl acrylate, and MEA is meant acrylic acid 2-methoxyl ethyl ester, and PEA is meant acrylic acid 2-phenoxy ethyl, and HEA is meant acrylic acid 2-hydroxy methacrylate, and AA is meant acrylic acid.
[table 1]
Then, the acryl resin of making more than expression is used prepares bonding agent and is applicable to the embodiment and the comparative example of blooming.Among the following embodiment and comparative example,, use compound shown below as ionic compound.
Ionic compound 1:N-octyl group-4-picoline hexafluorophosphate structure, the fusing point of following formula (have 44 ℃)
[changing 3]
Figure BPA00001309995900272
Two (trifluoromethane sulfonyl group) acid imides of ionic compound 2:N-hexyl-4-picoline structure, the fusing point of following formula (have 18 ℃)
[changing 4]
Figure BPA00001309995900273
Ionic compound 3: two (trifluoromethane sulfonyl group) acid imides of tricaprylmethylammonium (have the structure of following formula, be liquid at normal temperatures)
[changing 5]
Figure BPA00001309995900281
Ionic compound 4: two (trifluoromethane sulfonyl group) acid imides of tributyl-methyl phosphonium ammonium structure, the fusing point of following formula (have 28 ℃)
[changing 6]
Figure BPA00001309995900282
In addition, as crosslinking chemical and silane based compound, use material shown below (being trade name) respectively.
(crosslinking chemical)
CORONATE L: the ethyl acetate solution of the trimethylolpropane adduct of toluene diisocyanate (solid component concentration 75%), obtain from Japanese polyurethane Co., Ltd..
(silane compound)
KBM-403: glycidoxypropyltrime,hoxysilane (liquid), obtain from Shin-Etsu Chemial Co., Ltd.
[embodiment 1～8 and comparative example 1～6]
(a) manufacturing of bonding agent
With respect to each 100 parts of the solid constituents of the acryl resin A～J that obtains in the polymerization example 1～10, the ionic compound of the various amounts shown in the mixture table 2,0.5 part of silane based compound (KBM-403), and table 2 shown in the crosslinking chemical (CORONATE L) of various amounts mix, and then be that 13% mode is added ethyl acetate with solid component concentration, as adhesive composition.Crosslinking chemical (CORONATE L) is the ethyl acetate solution of solid component concentration 75% as mentioned above, and the addition shown in the table 2 is its solid constituent amount.
(b) making of band bonding agent blooming
The polyethylene terephthalate film that above-mentioned each adhesive composition is used applicator to be coated on the demoulding to handle (trade name " PET 3811 ", obtains from lintec Co., Ltd., be called diffusion barrier) demoulding treated side on, making dried thickness is 20 μ m, drying is 1 minute under 90 ℃, obtains the bonding agent of sheet.Then; on the face of the polarization plates of the 3-tier architecture that forms on the two sides of the polyvinyl alcohol (PVA) polaroid of using the diaphragm clamping absorption orientation iodine that constitutes by Triafol T; behind the face opposite (bonding agent face) of the sheet bonding agent that obtains more than pasting by lamination with diffusion barrier; health is 7 days under the condition of 23 ℃ of temperature, relative humidity 65%, obtains being with the bonding agent polarization plates.
(c) the antistatic behaviour evaluation of band bonding agent blooming
When peeling off the diffusion barrier of resulting band bonding agent polarization plates,, estimate antistatic behaviour with the sheet resistance value of surperficial intrinsic resistance determinator [" Hirest-up MCP-HT450 " (trade name) of Mitsubishi chemical Co., Ltd's system] mensuration bonding agent.Sheet resistance value is 10 11When Ω/ level or its are following, obtain good antistatic behaviour.
(d) making of optical laminate and evaluation
After the band bonding agent polarization plates of making from above-mentioned (b) peels diffusion barrier, its bonding agent face is pasted on liquid crystal cells uses the two sides of glass substrate [" 1737 " (trade name) of Corning corporate system] to form orthogonal polarization microscope, the making optical laminate.To this optical laminate, carry out 96 hours heat resistant test of keeping under the drying condition of 80 ℃ of temperature.Leakage when thereafter, visualization is from a polarization plates side incident light is white manifests state.The result with following benchmark classification, is shown in " leaking white (80 ℃ of dryings) " hurdle of table 2.
＜leak the white state that manifests 〉
1: do not leak white fully.
2: leak unobvious at all in vain.
3: leak obvious slightly in vain.
4: leak in vain clearly.
In addition, respectively to carrying out the situation (in table 2, being designated as " heat-resisting ") of 300 hours heat resistant test of keeping under the drying condition of 80 ℃ of temperature; Carry out situation (in table 2, being designated as " moisture-proof heat ") in 60 ℃ of temperature, 300 hours hot resistance test of 90% time keeping of relative humidity; To be cooled to-30 ℃ from the state that is heated to 70 ℃, then be warming up to 70 ℃ process as 1 circulation (1 hour) and repeat the situation (table 2, being designated as " anti-HS ") of 100 these round-robin heatproof impact tests, the optical laminate after the visualization test with carrying out.The result with following benchmark classification, is summarized in table 2.
(to the metewand of hot, damp and hot and thermal shock (in table 2, being designated as " heat-resisting ", " moisture-proof heat ", " anti-HS " respectively))
1: do not see fully heave, peel off, appearance change such as foaming.
2: almost do not see heave, peel off, appearance change such as foaming.
3: heave, peel off, appearance change such as foaming is obvious a little.
4: see significantly heave, peel off, appearance change such as foaming.
(e) the re-workability evaluation of band bonding agent blooming
The evaluation of re-workability is following to be carried out.At first, be the test film of 25mm * 150mm size with the band bonding agent polarization plates severing that obtains in above-mentioned (b).Then, use sticker (" Lamipacker " (trade name) of Fujipla Co., Ltd. system) to stick on liquid crystal cells with its binder side this test film, at 50 ℃, 5kg/cm with on the glass substrate 2Carrying out 20 minutes autoclaves (490.3kPa) handles.Then, under 70 ℃, carry out 2 hours heat treated, then in 50 ℃ baking oven, preserve after 48 hours, in the atmosphere of 23 ℃ of temperature, relative humidity 50%, from this stickup test film polarization plates is peeled off along 180 ° of directions with the speed that 300mm/ divides, the state on sight glass plate surface is classified according to following benchmark.The result together is shown in table 2.
The metewand of＜re-workability 〉
1: glass pane surface does not produce fuzzy etc. fully.
2: glass pane surface does not almost produce fuzzy etc.
3: the glass pane surface generation is fuzzy etc.
4: glass pane surface produces adhesive residue.
[table 2]
Figure BPA00001309995900311
By table 1 and table 2 as can be known, in the acryl resin of the present invention regulation, cooperate the ionic compound of ormal weight and crosslinking chemical and constitute the embodiment 1～8 of bonding agent antistatic behaviour, leak preventing property and re-workability excellence in vain, in addition, thermotolerance, humidity resistance and resistance to sudden heating also obtain roughly gratifying result.Particularly preventing property, re-workability, thermotolerance, humidity resistance and resistance to sudden heating are all excellent in vain for the antistatic behaviour of embodiment 2, leakage.
With respect to this, use the comparative example 1～3 contain from the acryl resin more than structural unit 20 weight portions of unsaturated monomer, and use and do not contain from the leakage of the comparative example 4 of the acryl resin of the structural unit of unsaturated monomer preventing property deficiency in vain with aromatic rings with aromatic rings.In addition, the comparative example 5 of gel fraction that does not reach the present invention regulation is heaved, is peeled off, appearance change such as foaming is all obvious in heat resistant test, hot resistance test and heatproof impact test.On the other hand, use leakage the preventing property deficiency in vain of the comparative example 6 of the big acryl resin of molecular weight distribution.
This disclosed embodiment and embodiment are illustration rather than qualification in all respects.Scope of the present invention is not above-mentioned explanation but is illustrated in claims, comprises the meaning that is equal to claim and all changes in the scope.
Utilizability on the industry
Of the present inventionly be endowed high antistatic behaviour with the adhesive blooming, simultaneously, keep for a long time this antistatic behaviour, in addition, durability is also excellent. This band adhesive blooming is preferred for liquid crystal indicator.
Symbol description
1 straight line polarizing coating, 2 surface-treated layers, 3 first diaphragms, 4 second diaphragms, 5 polarization plates, 7 phase retardation films, 8 interlayer adhesives, 10 bloomings, 20 comprise adhesive phase, 25 band adhesive bloomings, 30 liquid crystal cells (glass substrate), 40 optical laminates of ionic compound.

Claims (9)

1. a band bonding agent blooming is characterized in that,
Described band bonding agent blooming is that the one side at least at blooming forms adhesive phase and forms,
To have organic cation and fusing point be that the ionic compound below 80 ℃ and the adhesive composition of 0.01～5 weight portion (C) crosslinking chemical form to this adhesive phase by containing 100 weight portions (A) acryl resin, 0.2～8 weight portion (B), this adhesive phase has the gel fraction of 70～99 weight %
Described (A) acryl resin is by comprising the multipolymer that unsaturated monomer that has the two keys of an alkene and at least one aromatic rings in 80～96 weight % (A-1) (methyl) acrylate, 3～15 weight % (A-2) molecules and the monomer mixture that 0.1～5 weight % (A-3) has the unsaturated monomer of polar functional group obtain, and weight-average molecular weight (Mw) is 1,000,000～2,000,000, the molecular weight distribution shown in the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn is 3～7 acryl resin;
Described (A-1) (methyl) acrylate is (methyl) acrylate shown in the following formula (I),
[changing 1]
Figure FPA00001309995800011
In the formula, R 1Expression hydrogen atom or methyl, R 2Expression can be by the alkyl of the carbon number 1～14 of the alkoxy of carbon number 1～10 replacement.
2. band bonding agent blooming according to claim 1, wherein,
(A-2) unsaturated monomer that has the two keys of 1 alkene and at least one aromatic rings in the molecule is (methyl) acrylic monomers that contains aromatic rings shown in the following formula (II),
[changing 2]
Figure FPA00001309995800012
In the formula, R 3Expression hydrogen atom or methyl, n is 1～8 integer, R 4Expression hydrogen atom, alkyl, aralkyl or aryl.
3. band bonding agent blooming according to claim 1, wherein,
The polar functional group that described (A-3) has the unsaturated monomer of polar functional group is selected from free carboxy, hydroxyl, amino and epoxide ring.
4. band bonding agent blooming according to claim 3, wherein,
Described (C) crosslinking chemical contains the isocyanates based compound.
5. band bonding agent blooming according to claim 1, wherein,
The fusing point that described (B) has the organic cations ionic compound is more than 30 ℃.
6. band bonding agent blooming according to claim 1, wherein,
Adhesive composition also comprises 0.03～1 weight portion (D) silane based compound.
7. band bonding agent blooming according to claim 1, wherein,
Blooming is selected from polarization plates and phase retardation film.
8. band bonding agent blooming according to claim 1, wherein,
Surface at adhesive phase is pasted with stripping film.
9. an optical laminate is characterized in that,
The described band bonding agent of claim 1 blooming is laminated in glass substrate with its adhesive phase side.
CN200980131207.XA 2008-08-11 2009-08-07 Optical film with adhesive and optical laminate using same Active CN102119349B (en)

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