CN1958660A - Acrylic acid resin composition and adhesive - Google Patents
Acrylic acid resin composition and adhesive Download PDFInfo
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- CN1958660A CN1958660A CNA2006101436066A CN200610143606A CN1958660A CN 1958660 A CN1958660 A CN 1958660A CN A2006101436066 A CNA2006101436066 A CN A2006101436066A CN 200610143606 A CN200610143606 A CN 200610143606A CN 1958660 A CN1958660 A CN 1958660A
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- acrylic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Provided is an acrylic acid resin composition of an adhesive which does not generate appearance changes at optical laminated body and has excellent durability in the condition of high temperature and humidity and repeatedly heating and cooling. Relative to 100 part based on total amount of (1) and (2), (1) takes up 10 to 50 parts, wherein the relationship of the hydroxide concentration b of (1) and the hydroxide concentration b' of (2) and polar functional groups concentration c of the composition satisfies the follow formula: 6 <= [b/(b+b'+c)] <= 50. Methacrylate resin (a) as the main compositions of (1) contains 0.1 mol % to 10 mol % (b) which is acrylic resin having a molecular weight of 50000 to 500000. (a) as the main compositions of (2) contains 0.5 mol % to 8 mol % (c) which is acrylic resin having a molecular weight of 1000000 to 1500000. (b) is a monomer containing hydroxide and alkene double bond. (c) is a monomer containing polar functional groups and alkene double bond.
Description
Technical field
The present invention relates to acrylic acid resin composition and the tackiness agent that contains this acrylic acid resin composition.
Background technology
General employed liquid crystal cell in liquid crystal indicators such as TFT, STN has liquid crystal composition and is held in structure between the two sheet glass base materials.And, on this glass baseplate surface, by being the tackiness agent of main component with the acrylic resin, bloomings such as stacked polarization film, phase retardation film.And, laminated glass substrate, tackiness agent and blooming and the optical laminates that forms successively, general use at first is manufactured on blooming superimposed layer tackiness agent and the blooming that has tackiness agent that obtains, then in the method for the face superimposed layer glass baseplate of tackiness agent.
This has the blooming of tackiness agent, because under heat or wet heat condition, bigger by the flexible dimensional change that is caused, easy generation is curling etc., exist in foaming in the adhesive layer of resulting optical laminates, or produce between adhesive layer and the glass baseplate and problem such as arch upward, peel off.Further, act on the skewness one of the residual stress of the blooming that has tackiness agent under heat or wet heat condition, stress concentration results from the peripheral part of optical laminates, turns white thereby exist in to produce in the TN liquid crystal cell (TFT); In the stn liquid crystal box, produce the problem of irregular colour one.
In order to solve described problem, the spy opens and proposed in the 2000-109771 communique with weight-average molecular weight is that 600000～2000000 high-molecular-weight propylene acid resin and weight-average molecular weight are less than or equal to the acrylic acid resin composition that 500000 low molecular weight propylene acid resin constitutes.
Summary of the invention
Recently,, be used under the essential hot conditions, suppressing the interior foaming of adhesive layer when vehicle-mounted the thermotolerance of appearance change such as do not produce foaming, arch upward, peel off though, attempt to use liquid crystal indicator as vehicle mounteds such as auto-navigation systems; Do not produce anti-the turning white property of turning white under the hot conditions; The weather resistance of appearance change such as do not produce foaming under the super-humid conditions, arch upward, peel off; Even repeat heating cooling, the resistance to sudden heating (hereinafter being sometimes referred to as HS) of appearance change such as also do not produce foaming, arch upward, peel off.
The inventor, the optical laminates that tackiness agent superimposed layer blooming at the composition that comprises the high-molecular-weight propylene acid resin that satisfies the described condition of above-mentioned patent documentation fully and low molecular weight propylene acid resin is obtained is studied the back and is found, might be able to not satisfy thermotolerance, anti-turning white property, weather resistance and resistance to sudden heating.
The object of the present invention is to provide the acrylic acid resin composition of the tackiness agent of the optical laminates that is suitable for providing thermotolerance, anti-turning white property, weather resistance and resistance to sudden heating excellence.
In this case, the inventor has carried out studying intensively found that specific tackiness agent can solve described problem to tackiness agent, thereby finishes the present invention.
Promptly, acrylic acid resin composition of the present invention, it contains with the structural unit that derives from following monomer (a) (structural unit (a)) is main component, the structural unit (structural unit (b)) that contains the following monomer of deriving from of 0.1mol%～10mol% (b), the weight-average molecular weight that also can contain any composition of 0.01mol% or following monomer (c) still less conduct is 50000～500000 acrylic resin (1); Be main component with structural unit (a), the structural unit (c) that contains 0.5mol%～8mol%, the weight-average molecular weight that also can contain structural unit (b) is 1000000～1500000 acrylic resin (2), wherein with respect to total 100 weight parts of acrylic resin (1) and (2), contain 10 weight parts～50 parts by weight of acrylic resins (1), wherein the hydroxyl concentration that derives from structural unit (b) [b] that is contained in the acrylic resin (1), the relation of the polar functional group concentration [c] that derives from structural unit (c) that is contained in hydroxyl concentration that derives from structural unit (b) [b '] that is contained in the acrylic resin (2) and the acrylic resin (2) satisfies formula (I);
6°≤[b/(b+b′+c)]×100≤50...(I)
In the formula, the meaning of [b], [b '] and [c] is shown below;
(a): (methyl) acrylate shown in the following general formula (A)
In the formula, R
1Expression hydrogen atom or methyl, R
2The expression carbonatoms is 1～14 alkyl or aralkyl, R
2The hydrogen atom of alkyl or the hydrogen atom of aralkyl can be that 1～10 alkoxyl group replaces also by carbonatoms;
(b): intramolecularly contains the monomer of at least 1 hydroxyl and 1 olefinic double bond;
(c): intramolecularly contains at least 1 polar functional group being selected from carboxyl, amide group, amino, epoxy group(ing), oxetanyl, aldehyde radical and the isocyanate group and the monomer of 1 olefinic double bond.
The invention effect
Acrylic acid resin composition of the present invention, by controlling higher hydroxyl concentration in the low-molecular-weight acrylic resin (1), excellence aspect flexibility, and give tack with the excellence of blooming etc. to optical laminates.In addition, the blooming that has tackiness agent that the lamination blooming obtains with this tackiness agent for example, if be stacked on the glass substrate of liquid crystal cell, then provides optical laminates of the present invention.Described optical laminates because adhesive layer absorbs and to have relaxed under the wet heat condition, by the stress that dimensional change caused of blooming and glass substrate, can alleviate local stress concentration, and suppresses arching upward, peeling off for the adhesive layer of glass substrate.In addition, the optical defect owing to having prevented to be caused by inhomogenous stress distribution when glass substrate is TN liquid crystal cell (TFT), can suppress to turn white.
Further,, on the glass baseplate surface that joins with adhesive layer, also produce the residual etc. of gonorrhoea or tackiness agent hardly even after peeling off this film in order heavily to paste this blooming that has tackiness agent by optical laminates, that is, and the re-workability excellence.Thus, though will be once the blooming that has tackiness agent of lamination peeled off from the glass substrate of optical laminates, suppress the residual or gonorrhoea of tackiness agent on the surface of glass substrate that also can be after peeling off, and can be used as glass substrate once more.
Embodiment
Hereinafter, the present invention will be described in detail.
The monomer (a) that is used for acrylic resin of the present invention (1) and (2) is (methyl) acrylate shown in the general formula (A).
In the formula, R
1Expression hydrogen atom or methyl, R
2The expression carbonatoms is 1～14 alkyl or aralkyl.R
2The hydrogen atom of aralkyl or the hydrogen atom of alkyl can be that 1～10 alkoxyl group replaces also by carbonatoms.
Wherein, as monomer (a), for example can enumerate acrylate such as methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-EHA, vinylformic acid n-octyl, Isooctyl acrylate monomer, lauryl acrylate, stearyl acrylate ester, cyclohexyl acrylate, isobornyl acrylate, vinylformic acid benzene methyl, vinylformic acid methoxyl group ethyl ester and vinylformic acid oxyethyl group methyl esters; Methacrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid 2-ethylhexyl, n octyl methacrylate, Isooctyl methacrylate, lauryl methacrylate(LMA), methacrylic acid stearyl ester, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid benzene methyl, methacrylic acid methoxy base ethyl ester and methacrylic acid oxyethyl group methyl esters etc.
As monomer (a), can use different at least 2 kinds of monomers (a).
Content as the structural unit that derives from monomer (a) in the acrylic resin of the present invention (1) (structural unit (a)) is generally about 70mol%～99.9mol%, is preferably 90mol%～99.4mol%.Because if monomer (a) is less than or equal to 99.9mol%, the content that then derives from the structural unit (b) of monomer described later (b) increases, so the trend that the bonding position of existence and linking agent increases is preferred.
In addition, the content as the structural unit that derives from monomer (a) in the acrylic resin (2) (structural unit (a)) is generally about 70mol%～99.9mol%, is preferably 90mol%～99.4mol%.Because if monomer (a) is less than or equal to 99.9mol%, the content that then derives from the structural unit (c) of monomer described later (c) increases, so the trend that the bonding position of existence and linking agent increases is preferred.
Structural unit (b) is the necessary composition of acrylic resin (1), also can be used as any composition and is present in the acrylic resin (2).Wherein, monomer (b) contains the monomer of hydroxyl and 1 olefinic double bond for intramolecularly.
As monomer (b), for example can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester etc.In addition, can make up at least 2 kinds of different monomers (b) uses.
Structure monomer (b) in the acrylic resin (1) is necessary composition, as its content, is generally about 0.1mol%～10mol%.Because it is if the content of structural unit (b) is less than or equal to 10mol%, then cohesive force increases, and has the trend that arches upward, peels off or foam that suppresses between glass substrate and the adhesive layer, so preferred.Because it is if more than or equal to 0.1mol%, then flexibility increases, and has the trend that suppresses irregular colour one phenomenon, so preferred.
Structure monomer (b) in the acrylic resin (2) is any composition, as its content, is less than or equal to 10mol% usually.Because it is if the content of structural unit (b) is less than or equal to 10mol%, then cohesive force increases, and has the trend that arches upward, peels off or foam that suppresses between glass substrate and the adhesive layer, so preferred.
Structural unit (c) is the necessary composition of acrylic resin (2), though the content in acrylic resin (1) can preferably not contain in fact less than 0.01mol%.
Provide the monomer (c) of structural unit (c) to be selected from least 1 polar functional group in carboxyl, amide group, amino, epoxy group(ing), oxetanyl, aldehyde radical and the isocyanate group and the monomer of 1 olefinic double bond for intramolecularly contains.
Object lesson as monomer (c), as polar functional group is the monomer (c) of carboxyl, for example can enumerate, vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid etc. are the monomer (c) of amide group as polar functional group, for example can enumerate, acrylamide, Methacrylamide, N, N-dimethylaminopropyl acrylamide, diacetone diamide, N,N-DMAA, N, N-diethyl acrylamide, N hydroxymethyl acrylamide etc.
As polar functional group is the monomer (c) of epoxy group(ing), for example can enumerate glycidyl acrylate, glycidyl methacrylate, vinylformic acid 3,4-epoxycyclohexyl methyl esters, methacrylic acid 3,4-epoxycyclohexyl methyl esters etc.Wherein, such as vinylformic acid 3,4-epoxycyclohexyl methyl esters, methacrylic acid 3, Sauerstoffatoms such as 4-epoxycyclohexyl methyl esters constitute the monomer of 3 yuan of rings and 7 yuan of rings owing to have reactive higher epoxy group(ing), as monomer (c).
As polar functional group is the monomer (c) of oxetanyl, for example can enumerate (methyl) vinylformic acid oxetanyl ester, (methyl) vinylformic acid 3-oxetanyl methyl esters, (methyl) vinylformic acid (3-methyl-3-oxetanyl) methyl esters, (methyl) vinylformic acid (3-ethyl-3-oxetanyl) methyl esters etc.Further, as polar functional group is amino monomer (c), for example can enumerate vinylformic acid N, N-dimethylamino ethyl ester, allylamine etc., as polar functional group is the monomer (c) of isocyanate group, for example can enumerate, 2-methacryloxyethyl isocyanic ester etc. are the monomer (c) of aldehyde radical as polar functional group, for example can enumerate propenal etc.
As these monomers (c), though can make up different at least 2 kinds of monomers (c) uses, but owing in the polymerization of acrylic resin, produce gelation, preferably do not use the monomer (c) that contains the polar functional group that can react at least such as the combination etc. that contains the monomer (c) that is selected from a kind of polar functional group in amino and the epoxy group(ing) and contain the monomer (c) of isocyanate group simultaneously.
As monomer (c), wherein, being preferably polar functional group is the monomer (c) of carboxyl, is preferably vinylformic acid especially.
Content as the structural unit (c) that is contained in the acrylic resin of the present invention (2) is generally about 0.5mol%～8mol%.Because if the content of structural unit (c) is more than or equal to 0.5mol%, the trend that then has the cohesive force increase of resulting resin, so it is preferred, because if be less than or equal to 8mol%, even then the size of blooming changes, along with its dimensional change, tackiness agent also changes, difference between the brightness of the circumference of liquid crystal cell and the brightness of central part disappears, and the existence inhibition is turned white, the trend of irregular colour one phenomenon, so preferred.
Weight ratio (nonvolatile component) as the acrylic resin in the acrylic acid resin composition of the present invention (1) and (2), total 100 weight parts with respect to acrylic resin (1) and (2), acrylic resin (1) is generally 10 weight parts～50 weight parts, is preferably about 20 weight parts～40 weight parts.Because if acrylic resin (1) is more than or equal to 10 weight parts, even then the size of blooming changes, along with its dimensional change, adhesive layer also changes, difference between the brightness of the circumference of liquid crystal cell and the brightness of central part disappears, the existence inhibition is turned white, the trend of irregular colour one, so it is preferred, because if acrylic resin (1) is less than or equal to 50 weight parts, then improved the cementability under hot and humid, there is the trend that arches upward, peels off that reduces between glass substrate and the adhesive layer, and has the trend that improves re-workability, so preferred.
Acrylic acid resin composition of the present invention is total 100 weight parts with respect to acrylic resin (1) and acrylic resin (2), the acrylic acid resin composition that contains 10 weight parts～50 parts by weight of acrylic resins (1), wherein the relation of the polar functional group concentration [c] that derives from structural unit (c) that is contained in hydroxyl concentration that derives from structural unit (b) [b '] that is contained in the hydroxyl concentration that derives from structural unit (b) [b] that is contained in the acrylic resin (1), the acrylic resin (2) and the said composition satisfies formula (I);
6≤[b/(b+b′+c)]×100≤50 (I)
Wherein, [b/ (b+b '+c)] * 100 be preferably 6～30.
Wherein, the number that hydroxyl concentration [b] expression (the mmol number of the hydroxyl that derives from structural unit (b) that is contained in the acrylic resin (1)) obtains divided by (the g number of the acrylic resin composition of acrylic acid resin composition), the number that hydroxyl concentration [b '] expression (the mmol number of the hydroxyl that derives from monomer (b) that is contained in the acrylic resin (2)) obtains divided by (the g number of the acrylic resin composition of acrylic acid resin composition), the number that polar functional group concentration [c] expression (the mmol number of the polar functional group that derives from monomer (c) that is contained in the acrylic resin (2)) obtains divided by (the g number of the acrylic resin composition of acrylic acid resin composition).
And the acrylic resin composition of acrylic acid resin composition represents that acrylic resin (1) and (2) etc. contain the solid shape branch of the acrylic resin of structural unit (a).
[b/ (b+b '+c) * 100] more than or equal to 6, promptly, hydroxyl concentration [b] in the acrylic resin (1) was more than or equal to 6% o'clock of the total of the polar functional group concentration ([c]) in hydroxyl concentration in the resin combination ([b+b ']) and the acrylic resin (2) ([b+b '+c]), because the increased response of acrylic resin (1) and linking agent, the existence inhibition is turned white, the trend of irregular colour one phenomenon, so preferred.In addition, because if less than 50, then the cross-linking set of acrylic resin (1) reduces, cohesive force increases, and suppresses foaming easily, so preferred.
When the acrylic resin composition in the acrylic acid resin composition only was made of acrylic resin (1) and (2), concentration [b] can followingly be tried to achieve.
[b]＝(X1×Z1×Y1/100)/M1×1000/(X1+X2) (II)
X1: the consumption (g) (nonvolatile component) of acrylic resin (1)
X2: the consumption (g) (nonvolatile component) of acrylic resin (2)
Y1: the add-on (weight %) of the monomer (b) when acrylic resin (1) is made
M1: the molecular weight of employed monomer (b) when acrylic resin (1) is made
Z1: the hydroxyl value of employed per 1 molecule monomer (b) when acrylic resin (1) is made
And, when the monomer (b) in the acrylic resin (1) uses the n kind, if the hydroxyl concentration of i kind monomer (b) is expressed as [b]
i, then [b] can be expressed as:
When the acrylic resin composition in the acrylic acid resin composition only was made of acrylic resin (1) and (2), concentration [b '] can followingly be tried to achieve.
[b′]＝(X2×Z2×Y2/100)/M2×1000/(X1+X2) (III)
Y2: the add-on (weight %) of the monomer (b) when acrylic resin (2) is made
M2: the molecular weight of employed monomer (b) when acrylic resin (2) is made
Z2: the hydroxyl value of employed per 1 molecule monomer (b) when acrylic resin (2) is made
And, when the monomer (b) in the acrylic resin (2) uses the n kind, if the hydroxyl concentration of i kind monomer (b) is expressed as [b ']
i, then [b '] can be expressed as:
When the acrylic resin composition in the acrylic acid resin composition only was made of acrylic resin (1) and (2), concentration [c] can followingly be tried to achieve.
[c]＝(X2×Z3×Y3/100)/M3×1000/(X1+X2) (IV)
Y3: the add-on (weight %) of the monomer (c) when acrylic resin (2) is made
M3: the molecular weight of employed monomer (c) when acrylic resin (2) is made
Z3: the polar functional group number of employed per 1 molecule monomer (c) when acrylic resin (2) is made
And, when the monomer (c) in the acrylic resin (2) uses the n kind, if the hydroxyl concentration of i kind monomer (c) is expressed as [c]
i, then [c] can be expressed as:
When making among the present invention employed acrylic resin (1) and (2), further, can with monomer (a) and (b) different, intramolecularly contain that 1 olefinic double bond and 5 yuan encircle or monomer (d) polymerization together of more polynary ring ring texture.Wherein, as monomer (d), for example can enumerate, intramolecularly contains the monomer (hereinafter being sometimes referred to as the alicyclic ring monomer) of 1 olefinic double bond and alicyclic structure; Intramolecularly contains the monomer (hereinafter being sometimes referred to as heterocyclic monomer) of 1 olefinic double bond and heterocycle structure etc.
Alicyclic structure in the alicyclic ring monomer is commonly referred to as carbonatoms more than or equal to 5, and preferred carbonatoms is about 5～7 naphthenic hydrocarbon structure or cycloolefin structure.And, for the cycloolefin structure, contain olefinic double bond in the alicyclic structure.
Particularly, the monomer that contains 1 olefinic double bond and alicyclic structure as intramolecularly, can enumerate, isobornyl acrylate, cyclohexyl acrylate, vinylformic acid two cyclopentyl esters, vinylformic acid cyclo-dodecyl ester, vinylformic acid methyl cyclohexane ester, vinylformic acid 3-methyl cyclohexanol ester, vinylformic acid tertiary butyl cyclohexyl, cyclohexyl α ethoxy propylene acid esters, vinylformic acid cyclohexyl phenyl ester etc. have the acrylate of alicyclic structure; Isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid two cyclopentyl esters, methacrylic acid cyclo-dodecyl ester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid tertiary butyl cyclohexyl, cyclohexyl α ethoxyl methyl acrylate, methacrylic acid cyclohexyl phenyl ester etc. have the methacrylic ester of alicyclic structure etc.
As the alicyclic ring monomer, wherein, isobornyl acrylate, cyclohexyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, vinylformic acid two cyclopentyl esters are owing to obtain easily and preferably.
In addition,, can enumerate as the acrylate that contains a plurality of alicyclic structures, methylene-succinic acid dicyclohexyl methyl esters, methylene-succinic acid dicyclo monooctyl ester, succsinic acid dicyclo dodecyl methyl esters etc., vinyl acetate base cyclohexyl that contains vinyl etc. also is monomer (d).
Heterocycle structure in the heterocyclic monomer refers to carbonatoms more than or equal to 5, and preferred carbonatoms is that at least one methylene radical in 5～7 the alicyclic hydrocarbon radical is replaced the heterocyclic group that obtains by heteroatomss such as nitrogen-atoms, Sauerstoffatom or sulphur atoms.
Specifically, can enumerate acryloyl morpholine, caprolactam, N-vinyl 2-Pyrrolidone, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone modification tetrahydrofurfuryl acrylate etc.Further, as 2,5-dihydrofuran etc. are such, can contain olefinic double bond in heterocyclic group.Contain the monomer of 1 olefinic double bond and heterocycle structure as intramolecularly, wherein, be preferably N-vinyl pyrrolidone, caprolactam, acryloyl morpholine.
As monomer (d), can use different monomer (d).
As the content of the structural unit that derives from monomer (d) that is contained in acrylic resin of the present invention (1) or (2) (structural unit (d)),, be less than or equal to usually about 10 weight parts with respect to 100 parts by weight of acrylic resins.If contain structural unit (d), even then because the size of blooming changes, and along with its dimensional change, adhesive layer also changes, the difference between the brightness of the circumference of liquid crystal cell and the brightness of central part disappears, and might suppress to turn white, irregular colour one.
Further, when making among the present invention employed acrylic resin (1) and (2), also can be with vinyl monomer (e) polymerization.The monomer that vinyl monomer (e) refers to is different with monomer (a)～(d), intramolecularly has at least 1 vinyl, for example can enumerate vinyl ester, ethylene halide, vinylidene halide, conjugated diene compound, styrene monomer, nitrogenous aromatic ethenyl compound, (methyl) vinyl cyanide etc.
Wherein,, for example can enumerate single vinyl acetate such as vinyl-acetic ester, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate as vinyl ester; Divinyl esters such as hexanodioic acid divinyl ester, sebacic acid divinyl ester.
As ethylene halide, can enumerate vinylchlorid and bromine ethene etc., as vinylidene halide, can enumerate vinylidene chloride etc., as (methyl) vinyl cyanide, can enumerate vinyl cyanide, methacrylonitrile.
Conjugated diene compound is the alkene that intramolecularly has conjugated double bond,, can enumerate isoprene, divinyl, chloroprene etc. as object lesson.
As styrene monomer; can enumerate vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group vinylbenzene, fluorobenzene ethene, chloro-styrene, bromstyrol, Dowspray 9, iodobenzene ethene, nitrostyrolene, acetylbenzene ethene, methoxy styrene and Vinylstyrene etc.As nitrogenous aromatic ethenyl compound, for example can enumerate vinyl pyridine, vinylcarbazole etc.
As monomer (e), can use multiple different monomer (e).
The structural unit that derives from monomer (e) (e) that acrylic resin (1) or (2) are contained usually, with respect to acrylic resin 100 weight parts, is less than or equal to 5 weight parts, preferably is less than or equal to 0.05 weight part, is preferably in fact especially and does not contain.
Further, when making among the present invention employed acrylic resin (1) and (2), also can contain monomer (f) different with monomer (a)～(e), that intramolecularly has a plurality of olefinic double bonds.As monomer (f), for example can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, 1,3, (methyl) esters of acrylic acids such as 5-triacryl six hydrogen-S-triazine, tetramethylol methane tetraacrylate; Methylene radical two (methyl) acrylamide, ethylene (methyl) acrylamide, N, two (methyl) acrylic amides such as N-diallyl acrylamide; Allyl group (methyl) acrylate; Cyanacrylate; Triallylamine; Tetraallyl Pyromellitic Acid ester; N, N, N ', N '-tetraallyl-1,4-diaminobutane; Tetraallyl ammonium salt etc.
As monomer (f), can use multiple different monomer (f).
The structural unit that derives from monomer (f) (f) that acrylic resin (1) or (2) are contained usually, with respect to 100 parts by weight of acrylic resins, is less than or equal to 5 weight parts, preferably is less than or equal to 0.05 weight part, is preferably in fact especially and does not contain.
As the manufacture method of employed acrylic resin (1) among the present invention, for example can enumerate solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization etc.
In addition, in the manufacturing of acrylic resin (1), usually, use polymerization starter.Employed whole monomeric total 100 weight parts in the manufacturing with respect to acrylic resin (1), employed polymerization starter is about 0.1 weight part～5 weight parts.
As polymerization starter, can enumerate thermal polymerization or Photoepolymerizationinitiater initiater etc.,, for example can enumerate 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc. as Photoepolymerizationinitiater initiater.As thermal polymerization, for example can enumerate, 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl group valeronitrile), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2,2 '-azo two azo compounds such as (2-hydroxymethyl propionitrile); Laurylperoxide base, tertbutyl peroxide, benzoyl peroxide, tert butyl peroxy benzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di peroxy dicarbonate, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide trimethylacetic acid ester, peroxidation (3,5,5-trimethyl acetyl) organo-peroxide such as; Inorganic peroxides such as Potassium Persulphate, ammonium persulphate, hydrogen peroxide etc.In addition, and the redox class initiator of having used thermal polymerization and reductive agent etc. also can be used as polymerization starter.
As the manufacture method of acrylic resin (1), wherein be preferably solution polymerization process.Object lesson as solution polymerization process, can enumerate, mix desired monomer and organic solvent and prepare monomeric concentration more than or equal to 20 weight %, after being preferably the mixed solution of 30 weight %～60 weight %, under nitrogen atmosphere gas, add polymerization starter, about 40 ℃～90 ℃, preferably in the method etc. that stirs about 3 hours～10 hours about 60 ℃～80 ℃ down.In addition, in order to control reaction, add after can in polymerization, adding employed monomer, polymerization starter or being dissolved in organic solvent.
Wherein, as organic solvent, for example can enumerate, toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Ester such as ethyl acetate, butylacetate class; Aliphatics such as n-propyl alcohol, Virahol alcohols; Ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
As the molecular weight of the acrylic resin that so obtains (1), the weight-average molecular weight that obtains that converts of the polystyrene standard by gel permeation chromatography (GPC) is generally 50000～500000.Because if weight-average molecular weight is more than or equal to 50000, then exist to improve the cementability under hot and humid, reduce the trend that arches upward, peels off between glass substrate and the adhesive layer, and existence improves the trend of re-workability, so it is preferred, because if weight-average molecular weight is less than or equal to 500000, even then the size of blooming changes, along with its dimensional change, adhesive layer also changes, difference between the brightness of the circumference of liquid crystal cell and the brightness of central part disappears, and the existence inhibition is turned white, the trend of irregular colour one, so preferred.
As the manufacture method of employed acrylic resin (2) among the present invention, for example can enumerate solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization etc.Wherein, be preferably solution polymerization process.
Object lesson as solution polymerization process, can enumerate, mix desired monomer and organic solvent and prepare monomeric concentration more than or equal to 40 weight %, after being preferably the mixed solution of 50 weight %～60 weight %, under nitrogen atmosphere gas, add the polymerization starter about 0.001 weight part～0.2 weight part, about 40 ℃～90 ℃, preferably about 50 ℃～70 ℃, stir 8 hours or longer time down, preferably stir method about 10 hours～12 hours etc.
Employed polymerization starter in the acrylic resin (2), use with acrylic resin (1) in the identical polymerization starter of employed polymerization starter.In addition, as organic solvent, use with acrylic resin (1) in the identical organic solvent of employed organic solvent.
As the molecular weight of the acrylic resin that so obtains (2), the weight-average molecular weight (Mw) that obtains that converts of the polystyrene standard by gel permeation chromatography (GPC) is 1000000～1500000.Because if weight-average molecular weight is more than or equal to 1000000, then exist to improve the cementability under hot and humid, reduce the trend that arches upward, peels off between glass substrate and the adhesive layer, and existence improves the trend of re-workability, so it is preferred, because if weight-average molecular weight is less than or equal to 1500000, even then the size of blooming changes, along with its dimensional change, adhesive layer also changes, difference between the brightness of the circumference of liquid crystal cell and the brightness of central part disappears, and the existence inhibition is turned white, the trend of irregular colour one, so preferred.
Tackiness agent of the present invention cooperates linking agent to obtain in the acrylic acid resin composition that so obtains.Wherein employed linking agent intramolecularly have at least 2 can with hydroxyl and/or the crosslinked functional group of polar functional group contained in the acrylic resin (2), specifically, can enumerate isocyanate ester compound, epoxy compounds, metallo-chelate compounds and ethylene imine compounds etc.
Wherein, as isocyanate ester compound, for example can enumerate tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene multi-phenenyl isocyanate etc.In addition, make polyol reactions such as above-mentioned isocyanate compound and glycerine, TriMethylolPropane(TMP) and the adducts that obtains or 2,3 polymers of isocyanate compound etc. also can be used as linking agent in the present invention.
As epoxy compounds, for example can enumerate, the Resins, epoxy of bisphenol A-type, ethylene glycol glycidyl ether, polyethyleneglycol diglycidylether, glycerine diglycidyl ether, glycerine triglycidyl group ether, 1,6-hexylene glycol diglycidyl ether, trimethylolpropane tris glycidyl ether, diglycidylaniline, N, N, N ', N '-four glycidyl group m-xylene diamine and 1,3-two (N, N '-diglycidyl amino methyl) hexanaphthene etc.
As metal chelate compound, for example can enumerate coordination methyl ethyl diketone or methyl aceto acetate on polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium and compound of obtaining etc.
As the ethylene imine compounds; for example can enumerate; N; N '-ditan-4; 4 '-two (1-ethylene imine carbonyls), N, N '-Toluene-2,4-diisocyanate, 4-two (1-ethylene imine carbonyl), triethylene trimeric cyanamide, two isophthaloyl-1-(2-methyl ethylene imine), three-1-aziridinyl phosphine oxide, N; N '-hexa-methylene-1,6-two (1-ethylene imine carbonyl), TriMethylolPropane(TMP)-three-β-aziridinyl propionic ester and tetramethylol methane-three-β-aziridinyl propionic ester etc.
As linking agent, can use at least 2 kinds linking agent.As linking agent, wherein, isocyanate ester compound is because can be crosslinked and preferred with the structural unit (b) as the necessary composition of acrylic resin (1), particularly be selected from tolylene diisocyanate, make polyol reactions such as tolylene diisocyanate and glycerine or TriMethylolPropane(TMP) and at least a kind of linking agent of 3 polymers of 2 polymers of the adducts that obtains, tolylene diisocyanate and tolylene diisocyanate, because this hydroxyl and linking agent is reactive excellent, exists and suppress for the trend that arches upward, peels off of the adhesive layer of glass substrate and preferred.
As the consumption of the linking agent in the tackiness agent (nonvolatile component), with respect to acrylic resin 100 weight parts (nonvolatile component), be generally about 0.8 weight part～5 weight parts, be preferably about 1 weight part～3 weight parts.
Open as described in the 2000-109771 communique as the spy, specifically, total 100 weight parts (nonvolatile component) with respect to acrylic resin (1) and (2), though use 0.1 weight part and 0.15 parts by weight of cross-linking agent, but because if the amount of linking agent more than or equal to 0.8 weight part, then exist and suppress arching upward between glass substrate and the adhesive layer, the trend of peeling off and improving re-workability, so it is preferred, because if be less than or equal to 5 weight parts, then for the dimensional change of blooming, the tracing ability excellence of adhesive layer exists to reduce and turns white, so the trend of irregular colour one is preferred.
In the tackiness agent of the present invention,, preferably contain silane compound in order to improve the tack of adhesive layer and glass substrate.In addition, silane compound can be any one of monomer and oligopolymer.As the silane compound monomer, 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, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group dimethoxy-methyl silane, 3-glycidoxy propyl group oxyethyl group dimethylsilane etc.Oligopolymer as silane compound, can enumerate 3-sulfydryl propyl trimethoxy silicane-tetramethoxy-silicane oligopolymer, 3-sulfydryl propyl trimethoxy silicane-tetraethoxysilane oligopolymer, mercapto methyl Trimethoxy silane-tetramethoxy-silicane oligopolymer, mercapto methyl Trimethoxy silane-tetraethoxysilane oligopolymer, mercapto methyl triethoxyl silane-tetramethoxy-silicane oligopolymer, mercapto methyl triethoxyl silane-tetraethoxysilane oligopolymer, 3-methacryloxypropyl trimethoxy silane-tetramethoxy-silicane oligopolymer, 3-acryloxy propyl trimethoxy silicane-tetramethoxy-silicane oligopolymer, vinyltrimethoxy silane-tetramethoxy-silicane oligopolymer, 3-TSL 8330-tetramethoxy-silicane oligopolymer etc.
Can use at least 2 kinds of silane compounds in the tackiness agent of the present invention.
As the consumption (solution) of the silane compound in the tackiness agent, with respect to acrylic acid resin composition 100 weight parts (nonvolatile component), usually, use about 0.0001 weight part～10 weight parts, preferably use the amount of 0.01 weight part～5 weight parts.Because if the amount of silane compound is more than or equal to 0.0001 weight part, then the tack of adhesive layer and glass substrate increases, so preferred.In addition, owing to, then exist and suppress the trend that silane compound oozes out from adhesive layer, so preferred if the amount of silane compound is less than or equal to 10 weight parts.
As mentioned above, tackiness agent of the present invention contains acrylic resin (1), acrylic resin (2) and linking agent, preferably also contain silane compound, further, also can cooperate crosslinking catalyst, weather-proof stablizer, tackifier, softening agent, tenderizer, dyestuff, pigment and inorganic filler etc.
Wherein, if in tackiness agent, cooperate crosslinking catalyst and linking agent, then can prepare the blooming that has tackiness agent by the slaking of short period of time, for the optical laminates that contains this film, can suppress between blooming and the adhesive layer arch upward, peel off or adhesive layer in foaming, and re-workability might be excellent.
As crosslinking catalyst, for example can enumerate aminated compoundss such as hexamethylene-diamine, quadrol, polymine, vulkacit H, diethylenetriamine, Triethylenetetramine (TETA), isophorone diamine, triethylenediamine, poly-aminoresin and melamine resin etc.When using amine compound as crosslinking catalyst in the tackiness agent, preferably use isocyanate ester compound as linking agent.
The blooming that has tackiness agent of the present invention is film formed by above-mentioned tackiness agent and optics, as its manufacture method, can enumerate for example following method: coating is diluted in the tackiness agent in the organic solvent on stripping film, heating was distilled and is removed organic solvent in about 0.5 minute～10 minutes under 60 ℃～120 ℃, obtained adhesive layer.Then, behind applying blooming on the adhesive layer, if be that 23 ℃, humidity are under 65% the atmosphere gas in temperature, then slaking about 5 days～20 days, linking agent is fully reacted after, peel off the method that stripping film obtains having the blooming of tackiness agent; With above-mentioned similarly obtain adhesive layer after, stripping film and adhesive layer are replaced after 2 layer laminate bodies with resulting stripping film and adhesive layer are combined as multilayer, if in temperature is that 23 ℃, humidity are under 65% the atmosphere gas, then slaking is about 5 days～20 days, after linking agent is fully reacted, not to peel off stripping film but the applying blooming, further peel off the method etc. that stripping film obtains having the blooming of tackiness agent.
Wherein, stripping film is the base material when forming adhesive layer.It also may be the base material that the protection adhesive layer is not subjected to impurity effect such as dust when preserving in slaking or as the blooming that has tackiness agent.Object lesson as stripping film, can enumerate, with the film that contains various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyacrylic ester is base material, on the adhesive face of this base material and adhesive layer, implement that (siloxane treated etc.) are handled in the demoulding and the stripping film that obtains etc.
Employed blooming refers to the film with optical characteristics in the blooming that has a tackiness agent of the present invention, can enumerate for example polarization film, phase retardation film etc.Polarization film is the incident light for natural light etc., the blooming with function of outgoing polarized light.As polarization film, can enumerate, have the rectilinearly polarized light that absorbs the vibration plane be parallel to optic axis, see through the rectilinearly polarized light film of character of the rectilinearly polarized light of the vibration plane that vertical surface is arranged; Reflect the polarized light separation membrane of the rectilinearly polarized light of the vibration plane that is parallel to optic axis; Stacked polarization film and phase retardation film described later and elliptically polarized light film of obtaining etc.As the object lesson of polarization film, can enumerate dichroism pigment such as the polyvinyl alcohol film of uniaxial extension absorption orientation iodine, dichroic dye and the film that obtains etc.
Phase retardation film refers to optically anisotropic bloomings such as having single shaft or twin shaft; for example can enumerate, be stretched to stretched film that obtains about 1.01 times～6 times etc. by the polymeric membrane that will contain polyvinyl alcohol, polycarbonate, polyester, polyacrylic ester, polyimide, polyolefine, polystyrene, polysulfones, polyethersulfone, poly(vinylidene fluoride)/polymethylmethacrylate, liquid crystal polyester, ethanoyl Mierocrystalline cellulose, cyclic polyolefin, ethylene-acetidin copolymer saponification material, polyvinyl chloride etc.Wherein, be preferably polycarbonate or polyvinyl alcohol uniaxial extension, the biaxial stretch-formed and polymeric membrane that obtains.
As phase retardation film, can enumerate uniaxiality phase retardation film, Wide-angle phase retardation film, low light spring rate phase retardation film, temperature compensating type phase retardation film, LC film (rod shaped liquid crystal twist alignment), WV film (discoid liquid crystal tilted alignment), NH film (rod shaped liquid crystal tilted alignment), VAC film (diaxial orientation type phase retardation film fully), newVAC film (diaxial orientation type phase retardation film) etc.
The blooming that further preferably uses further adhesive substrates film (protective membrane) on the one or both sides of these bloomings and obtain is as blooming.As substrate film; for example can enumerate ethanoyl cellulose family film, polyester resin film, olefin resin film, polycarbonate resin adipose membrane, polyether-ether-ketone resin film, polysulfone resin films etc. such as the acrylic resin film different, tri cellulose acetate membrane with acrylic resin of the present invention.In substrate film, also can cooperate UV light absorber such as bigcatkin willow acid esters compound, benzophenone compound, benzotriazole compound, compound in triazine class, cyanoacrylate compound, nickel chelating salt compounds.In the substrate film, be preferably ethanoyl cellulose family film.
Optical laminates of the present invention is to be formed by blooming that has tackiness agent and glass substrate.
Can fit the usually adhesive layer and the glass substrate of the blooming that has tackiness agent of optical laminates made.Wherein,, for example can enumerate as glass substrate, the glass substrate of liquid crystal cell, anti-dazzle with glass, sun glasses with glass etc.Wherein, the adhesive layer of the blooming (upper polarizing sheet) that has tackiness agent owing on the glass substrate on the top of liquid crystal cell, fit, on the glass substrate of the bottom of liquid crystal cell, fit other the adhesive layer of the blooming that has tackiness agent (lower polarizing sheet) and the optical laminates that forms can be as liquid crystal indicator and preferred.As the material of glass substrate, for example can enumerate soda-lime glass, glass with lower alkali content, non-alkali glass etc.
Optical laminates of the present invention, even after peeling off the blooming that has tackiness agent from optical laminates, on the glass baseplate surface that joins with adhesive layer, the residual etc. of gonorrhoea or tackiness agent also taken place hardly, so can easily on the glass substrate of being stripped from, heavily paste the blooming that has tackiness agent once more, that is re-workability excellence.
Embodiment
Hereinafter, enumerate embodiment the present invention is carried out more specific description.And, " part ", " % " among the embodiment, only otherwise special the qualification refers to weight basis.In addition, nonvolatile component is by measuring based on the measuring method of JIS K-5407.Specifically, get the adhesive solvent of any weight, represent with respect to the ratio of the weight of the solution of initial mensuration with the residual nonvolatile component weight of 115 ℃ of following dryings after 2 hours in the explosion-proof baking oven with ware.Viscosity is 25 ℃ of values of passing through the Brookfield viscometer determining down.Weight-average molecular weight is measured and is to use device to convert by polystyrene standard, is that 5mg/ml, sample import volume are 100 μ ml, use eastern ソ one (strain) to make: TSKgelG6000H at sample concentration
XL2, TSKgelG5000H
XL2 pillars that are connected in series successively are as chromatographic column, are that 40 ℃, flow velocity are under the condition of 1ml/min in temperature, use tetrahydrofuran (THF) to try to achieve as elutriant.
The Production Example of＜acrylic resin 〉
(polymerization example 1)
In reactor with cooling tube, nitrogen ingress pipe, thermometer, stirrer, add 222 parts of ethyl acetate, the air with in the nitrogen replaceable equipment behind the oxygen-free gas, is warming up to 75 ℃ with interior temperature.Full dose is added behind 0.55 part of solution that is dissolved in 12.5 parts of ethyl acetate and obtains of Diisopropyl azodicarboxylate (AIBN hereinafter referred to as), when interior temperature is remained in 69 ℃～71 ℃, in 3 hours, will drip in reaction system as 44 parts of 36 parts of butyl acrylates, the butyl methacrylate of monomer (a), the mixing solutions of 20 parts of methyl acrylates.Then, be 69 ℃～71 ℃ in interior temperature and be incubated 5 hours down, finish reaction.The weight-average molecular weight of the polystyrene conversion of GPC is 100000.
(polymerization example 2～7)
Form with the monomer shown in the table 1, similarly operate with polymerization example 1 basically and finish reaction.
[table 1]
| Monomer is formed (weight part) | Mw ×10.000 | |||||
| BA(a) | BMA(a) | MA(a) | 2HEA(b) | AA(c) | ||
| Polymerization example 1 | 36 | 44 | 20 | 0 | 0 | 10 |
| Polymerization example 2 | 35.2 | 44 | 20 | 0.8 | 0 | 10 |
| Polymerization example 3 | 35 | 44 | 20 | 1 | 0 | 9 |
| Polymerization example 4 | 31.2 | 44 | 20 | 4.8 | 0 | 8 |
| Polymerization example 5 | 99.5 | 0 | 0 | 0.5 | 0 | 10 |
| Polymerization example 6 | 35.5 | 44 | 20 | 0 | 0.5 | 10 |
| Polymerization example 7 | 99.5 | 0 | 0 | 0 | 0.5 | 5 |
BA: butyl acrylate, BMA: butyl methacrylate
MA: methyl acrylate, 2HEA: 2-Hydroxy ethyl acrylate
AA: vinylformic acid
(polymerization example 8)
Adding is as 99 parts of the butyl acrylates of monomer (a), as the mixing solutions of 1.0 parts in the vinylformic acid of monomer (c), with the air in the nitrogen replaceable equipment, when making oxygen-free gas, after interior temperature was warming up to 65 ℃, full dose was added the solution that 0.2 part AIBN is dissolved in 10 parts of ethyl acetate and obtains.Then, be 65 ℃ of down insulations 6 hours in interior temperature, in 1 hour, drip the solution that 0.4 part AIBN is dissolved in 20 parts of ethyl acetate and obtains then, further reacted 2 hours, finish polymerization.The weight-average molecular weight of the polystyrene conversion of GPC is 1150000, and Mw/Mn is 8.0.
(polymerization example 9)
In the reactor identical with polymerization example (8), the mixing solutions that adds 81.8 parts of acetone, 98.9 parts of butyl acrylates (BA hereinafter referred to as), 1.1 parts of vinylformic acid (AA hereinafter referred to as) as monomer (c) as monomer (a), with the air in the nitrogen replaceable equipment, when making oxygen-free gas, after interior temperature was warming up to 55 ℃, full dose was added the solution that 0.14 part Diisopropyl azodicarboxylate (AIBN hereinafter referred to as) is dissolved in 10 parts of acetone and obtains.Add initiator after 1 hour, for the concentration (hereinafter being sometimes referred to as reaction density) of the acrylic resin that makes demonomerization is 35 weight %, with 17.3 weight parts/hour interpolation speed when acetone soln is made an addition to reactor continuously, be 54 ℃～56 ℃ in interior temperature and be incubated 12 hours down, add ethyl acetate solvent at last reaction density is adjusted to 20%.Weight-average molecular weight is 1200000, and Mw/Mn is 3.9.
(polymerization example 10)
In the reactor identical with polymerization example (8), add the butyl acrylate of 80 parts of acetone, 95 parts of conducts (a), 5 parts of acrylic acid mixing solutionss as monomer (c), with the air in the nitrogen replaceable equipment, when making oxygen-free gas, after interior temperature was warming up to 55 ℃, full dose was added the solution that 0.1 part AIBN is dissolved in 3 parts of acetone and obtains.Then, insulation dripped acetone after 1 hour in 6 hours under interior temperature is 55 ℃, further reacted 4 hours, finished polymerization.The weight-average molecular weight of the polystyrene conversion of GPC is 1570000, and Mw/Mn is 3.4.
Monomer ratio of components, molecular weight and the molecular weight distribution of polymerization example 8～10 are as shown in table 2.
[table 2]
| Monomer is formed (weight part) | Mw ×10.000 | Mw/Mn | ||
| BA(a) | AA(c) | |||
| Polymkeric substance 8 | 99 | 1 | 115 | 8 |
| Polymkeric substance 9 | 98.9 | 1.1 | 120 | 3.9 |
| Polymkeric substance 10 | 95 | 5 | 157 | 3.4 |
BA: butyl acrylate, AA: vinylformic acid
(embodiment 1)
The Production Example of＜tackiness agent 〉
With weight ratio mixing acrylic resin (1) and (2) of table 3, obtain the ethyl acetate solution of acrylic acid resin composition.In 100 parts of the nonvolatile component of resultant solution, mixing is as the adducts (trade(brand)name: コ ロ ネ one ト L of the tolylene diisocyanate of linking agent, Japanese polyurethane industry system) 2 parts of (nonvolatile component), silane compound (trade(brand)names: Y11597, DowCorning Toray system) 0.1 part, obtains tackiness agent of the present invention.
＜have a Production Example of the blooming and the optical laminates of tackiness agent 〉
Making dried thickness is that the tackiness agent that 25 μ m use coating machine so to obtain is coated polyethylene terephthalate film (the リ Application テ Star Network corporate system of handling through the demoulding, trade(brand)name: on demoulding treated side PET3811), drying is 1 minute under 90 ℃, obtains flaky tackiness agent.Then; use polarization film (having the film of 3-tier architecture that clips the two sides of the film that makes iodine be adsorbed in polyvinyl alcohol and stretching and obtain with tri acetyl cellulose class protective membrane) as blooming; on this blooming; by laminator fit have the face of above-mentioned resulting tackiness agent after; in temperature is that 23 ℃, humidity are slaking 10 days under 65% the condition, obtains being provided with the blooming that has tackiness agent of adhesive layer.Then, the polarizer that is orthogonal on the two sides of liquid crystal cell with glass substrate (Corning corporate system, 1737) is fixed in this blooming stickup that has tackiness agent, obtains optical laminates.Based on following main points to they estimate, the fractionated result is as shown in table 4.
The turning white property of＜optical laminates 〉
The evaluation that goes out present condition of turning white of under 80 ℃, drying optical laminates being preserved after 96 hours is carried out with following 4 grades.
◎: do not see fully and turn white.
Zero: it is not obvious basically to turn white.
△: it is obvious a little to turn white.
*: turn white significantly.
The humidity resistance of＜optical laminates 〉
The evaluation of optical laminates being preserved the appearance change after 96 hours under 60 ℃, 90%RH is carried out with following 4 grades.
◎: do not see fully arch upward, peel off, appearance change such as foaming.
Zero: almost do not see arch upward, peel off, appearance change such as foaming.
△: arch upward, peel off, appearance change such as foaming is obvious a little.
*: arch upward, peel off, appearance change such as foaming is remarkable.
The thermotolerance of＜optical laminates 〉
The evaluation of optical laminates being preserved the appearance change after 96 hours under 80 ℃, drying is carried out with following 4 grades.
◎: do not see fully arch upward, peel off, appearance change such as foaming.
Zero: almost do not see arch upward, peel off, appearance change such as foaming.
△: arch upward, peel off, appearance change such as foaming is obvious a little.
*: arch upward, peel off, appearance change such as foaming is remarkable.
The resistance to sudden heating of＜optical laminates (anti-HS) 〉
After optical laminates is heated to 60 ℃, being cooled to-20 ℃, further being warming up to 60 ℃, is 1 circulation (1 hour) with this process, preserves the evaluation of the appearance change after 100 circulations and carries out with following 4 grades.
◎: do not see fully arch upward, peel off, appearance change such as foaming.
Zero: almost do not see arch upward, peel off, appearance change such as foaming.
△: arch upward, peel off, appearance change such as foaming is obvious a little.
*: arch upward, peel off, appearance change such as foaming is remarkable.
＜re-workability 〉
The evaluation of re-workability is following to be carried out.At first, the above-mentioned optical laminates of preparation in the test film of 25mm * 150mm.Then, use laminating apparatus (Fuji's プ ラ ス チ Star Network machinery (strain) system " ラ ミ パ Star カ one ") that this test film is pasted on liquid crystal cell with on the glass substrate, under 50 ℃ with 5kg/cm
2(490.3kPa) carrying out 20 minutes high-voltage devices handles.Then, after carrying out 2 hours heat treated under 70 ℃, in 50 ℃ baking oven, preserve after 48 hours, at 23 ℃, relative humidity is that the speed with 300mm/min is peeled off this stickups fixed test film in the 50%RH atmosphere gas on 180 degree directions, and observation is as shown in table 4 with the result of the following state that will put the fractionated glass pane surface.
By the state of glass pane surface, the evaluation of re-workability is carried out with following 4 grades.
◎: on glass pane surface, do not see the residual of gonorrhoea and tackiness agent fully.
Zero: on glass pane surface, almost do not see gonorrhoea etc.
△: on glass pane surface, find gonorrhoea etc.
*: on glass pane surface, find to have the residual of tackiness agent.
(embodiment 2～5 comparative examples 1～7)
According to embodiment 1, mix acrylic resin (1) and (2) with the weight ratio shown in the table 3, obtain the ethyl acetate solution of acrylic acid resin composition.In 100 parts of the nonvolatile component of resulting solution, mixed cross-linker and silane compound obtain tackiness agent of the present invention.
The mixed weight of acrylic resin (1) and (2) than, linking agent kind and amount, silane compound kind and measure as shown in table 3.
[table 3]
The meaning of M1 in the table 3, M3, X1, X2, Y1, Y3, Z1 and Z3 is as follows, [b], [c], [b]/([b]+[b ']+[c]) * 100 can through type (II) and formula (III) try to achieve.And, owing to do not use monomer (b), [b ']=0 in the acrylic resin (2).
[b]＝([X1×Z1×Y1/100]/M1)×1000/(X1+X2) (II)
X1: the consumption (g) (nonvolatile component) of acrylic resin (1)
X2: the consumption (g) (nonvolatile component) of acrylic resin (2)
Y1: the add-on (weight %) of the monomer (b) when acrylic resin (1) is made
M1: the molecular weight of employed monomer (b) when acrylic resin (1) is made
Z1: the hydroxyl value of employed per 1 molecule monomer (b) when acrylic resin (1) is made
[c]＝([X2×Z3×Y3/100]/M3)×1000/(X1+X2) (IV)
Y3: the add-on (weight %) of the monomer (c) when acrylic resin (2) is made
M3: the molecular weight of employed monomer (c) when acrylic resin (2) is made
Z3: the polar functional group number of employed per 1 molecule monomer (c) when acrylic resin (2) is made
The abbreviation of the silane compound in the table 3 is as follows.
コ ロ ネ one ト L: the adducts コ ロ ネ one ト L of Japanese polyurethane industry (strain) preparing methylbenzene vulcabond
D-110N: military field chemical (strain) the preparing methylbenzene vulcabond adducts " ケ ネ one ト D-110N " of Mitsui
Y11597:Dow Corning Toray (strain) makes silane agent " Y11597 "
X-41-1805: believe chemical industry system siloxanes alkoxyl group oligopolymer " X-41-1805 " more
KBM403: believe chemical industry system silane coupling agent " KBM403 " more
[table 4]
Utilizability on the industry
Acrylic acid resin composition of the present invention is such as the main component that can be used as the adhesive that is suitable for the optical laminates such as TN liquid crystal cell (TFT). In addition, if with the adhesive of composition of the present invention for the stn liquid crystal box, then can suppress the irregular colour one of resulting optical laminates.
Claims (13)
1. acrylic acid resin composition, it contains:
With the structural unit (structural unit (a)) that derives from following monomer (a) is main component, the structural unit (structural unit (b)) that contains the following monomer of deriving from of 0.1mol%～10mol% (b), the weight-average molecular weight that also can contain any composition of 0.01mol% or following monomer (c) still less conduct is 50000～500000 acrylic resin (1); With
(a) is main component with structural unit, contains the structural unit (c) of 0.5mol%～8mol%, and the weight-average molecular weight that also can contain structural unit (b) is 1000000～1500000 acrylic resin (2),
Total 100 weight parts with respect to acrylic resin (1) and (2), contain 10 weight parts～50 parts by weight of acrylic resins (1), wherein the relation of the polar functional group concentration [c] that derives from structural unit (c) that is contained in hydroxyl concentration that derives from structural unit (b) [b '] that is contained in the hydroxyl concentration that derives from structural unit (b) [b] that is contained in the acrylic resin (1), the acrylic resin (2) and the acrylic resin (2) satisfies formula (I);
6≤[b/(b+b′+c)]×100≤50…(I)
In the formula, the meaning of [b], [b '] and [c] is shown below;
(a): (methyl) acrylate shown in the following general formula (A),
In the formula, R
1Expression hydrogen atom or methyl, R
2The expression carbonatoms is 1～14 alkyl or aralkyl, R
2The hydrogen atom of alkyl or the hydrogen atom of aralkyl can be that 1～10 alkoxyl group replaces also by carbonatoms;
(b): intramolecularly contains the monomer of at least 1 hydroxyl and 1 olefinic double bond;
(c): intramolecularly contains at least 1 polar functional group being selected from carboxyl, amide group, amino, epoxy group(ing), oxetanyl, aldehyde radical and isocyanate group and the monomer of 1 olefinic double bond.
2. acrylic acid resin composition as claimed in claim 1, wherein, the polar functional group that derives from structural unit (c) that is contained in the described acrylic resin (2) is a carboxyl.
3. tackiness agent, it cooperates claim 1 or 2 described acrylic acid resin compositions and linking agent and forms.
4. tackiness agent as claimed in claim 3, wherein, described linking agent is the isocyanates linking agent.
5. tackiness agent as claimed in claim 4, wherein, described linking agent is to be selected from tolylene diisocyanate, to make tolylene diisocyanate and polyol reaction and at least a kind of linking agent of 3 polymers of 2 polymers of the adducts that obtains, tolylene diisocyanate and tolylene diisocyanate.
6. as any described tackiness agent of claim 3～5, it is characterized in that it further contains silane compound.
7. the blooming that has tackiness agent, its two sides or any described tackiness agent of superimposed layer claim 3～6 at blooming forms.
8. the blooming that has tackiness agent as claimed in claim 7, wherein, described blooming is polarization film and/or phase retardation film.
9. as claim 7 or the 8 described bloomings that have tackiness agent, wherein, described blooming is further to paste the blooming that fixing ethanoyl cellulose family film forms as protective membrane.
10. as any described blooming that has tackiness agent of claim 7～8, its further lamination stripping film on the adhesive layer of the blooming that has tackiness agent forms.
11. optical laminates, it forms at any described adhesive layer superimposed layer glass baseplate that has the blooming of tackiness agent of claim 7～8.
12. optical laminates, it is after the Accessory Right requirement 10 described bloomings that have tackiness agent are peeled off stripping film, and the adhesive layer superimposed layer glass baseplate that obtains forms peeling off.
13. optical laminates, it is after Accessory Right requirement 11 described optical laminates are peeled off the blooming that has tackiness agent, and blooming that lamination has tackiness agent forms peeling off on the glass baseplate that obtains once more.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005320516A JP5023470B2 (en) | 2005-11-04 | 2005-11-04 | Acrylic resin composition and pressure-sensitive adhesive |
| JP2005320516 | 2005-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1958660A true CN1958660A (en) | 2007-05-09 |
Family
ID=38070523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101436066A Pending CN1958660A (en) | 2005-11-04 | 2006-11-02 | Acrylic acid resin composition and adhesive |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5023470B2 (en) |
| KR (1) | KR101288238B1 (en) |
| CN (1) | CN1958660A (en) |
| TW (1) | TWI406898B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101288238B1 (en) | 2013-07-26 |
| KR20070048600A (en) | 2007-05-09 |
| TW200738812A (en) | 2007-10-16 |
| JP5023470B2 (en) | 2012-09-12 |
| TWI406898B (en) | 2013-09-01 |
| JP2007126559A (en) | 2007-05-24 |
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