CN109021478A - (methyl) acrylic resin composition and (methyl) acrylic resin film for using the composition - Google Patents

Abstract

The present invention provides (methyl) acrylic resin composition, (methyl) acrylic resin film and its stretched film using the composition and the polarization plates including being somebody's turn to do (methyl) acrylic resin film or its stretched film and polarizing coating of a kind of (methyl) acrylic resin B that and weight average molecular weight low with the glass transition temperature than (methyl) acrylic resin A comprising (methyl) acrylic resin A is 100000 or more.

Description

(methyl) acrylic resin composition and (methyl) acrylic acid for using the composition Resin film

The application be applicant submit application No. is 201410602491.7, entitled " (methyl) acrylic acid series The divisional application of the application of resin combination and (methyl) acrylic resin film for using the composition ".Parent application day is On October 31st, 2014, priority date are on October 31st, 2013.

Technical field

The present invention relates to (methyl) acrylic resin composition and use (methyl) acrylic resin of the composition Film.In addition, the invention further relates to the polarization plates with (methyl) acrylic resin film.

Background technique

In recent years, electric quantity consumption is small, work at low voltage, light weight and slim liquid crystal display device are in mobile phone, portable It is widely applied in the device for display of message such as information terminal, the display of computer, TV.Such device for display of message according to The difference on way and require the reliability under harsh environment.For example, for auto-navigation system liquid crystal display device and Speech, place its interior temperature, humidity becomes very high sometimes, with common TV, PC display compared with, It is required that temperature and damp condition it is more stringent.And in liquid crystal display device, polarization is used in order to show When plate, in the liquid crystal display device for requiring such stringent temperature and/or humidity condition, the polarization plates for constituting it are also wanted It asks with high-durability.

Polarization plates usually have the two of the polarizing coating being made of the polyvinyl alcohol resin of dichroism pigment gas absorption quantity Face or single side are laminated with the structure of transparent protective film.And triacetyl cellulose is widely used in the protective film all the time Element, the protective film are Nian Jie with polarizing coating by the inclusion of the bonding agent of the aqueous solution of polyvinyl alcohol resin.But for being laminated with For the polarization plates of protective film comprising triacetyl cellulose, since the moisture permeability of triacetyl cellulose is high, high damp and hot For a long time in use, polarization property reduction sometimes or protective film and polarizing coating are peeling-off under environment.

Thus, for example attempting will be with tri acetyl cellulose membrane as recorded in Japanese Unexamined Patent Publication 2011-123169 bulletin (methyl) acrylic resin film lower compared to moisture permeability is used as the protective film of polarization plates.Pass through (methyl) that moisture permeability is low Acrylic resin film is used as the protective film of polarization plates, it is contemplated that the moisture-proof of polarization plates can be improved.

But since the toughness of (methyl) acrylic resin film (flexibility) is poor, be easily broken off, it is squeezed by melting It when being filmed out, is broken sometimes when carrying out stretch processing to film made of film, or damaged or notch occurs.If generating broken Then there is the risk of fragment pollution manufacturing process in damage, notch.

It describes in Japanese Unexamined Patent Application 63-077963 bulletin and Japanese Unexamined Patent Publication 2012-018383 bulletin by (first Base) compound rubber elastomer particle in acrylic resin, system when can be improved impact resistance when film has been made, being made film Film property.According to this method, the impact resistance of (methyl) acrylic resin film can be improved, can be improved toughness.But if rubber Glue elastomer particle it is more containing quantitative change, then the heat shrink that there is film becomes larger, the not only heat resistance of film but also using the inclined of the film The risk that the heat resistance of vibration plate reduces.

Summary of the invention

The purpose of the present invention is to provide be capable of forming (methyl) third for showing the small film of good toughness, heat shrink rate Olefin(e) acid based resin composition and (methyl) acrylic resin film for using the composition.In addition, another object of the present invention exists There are the polarization plates for being somebody's turn to do (methyl) acrylic resin film in providing.

The present invention provides (methyl) acrylic resin composition as shown below, (methyl) acrylic resin film, drawing Stretch film and polarization plates.

[1] a kind of (methyl) acrylic resin composition, it includes:

(methyl) acrylic resin A and

And weight average molecular weight lower than the glass transition temperature of shown (methyl) acrylic resin A is 100000 or more (methyl) acrylic resin B.

[2] (methyl) acrylic resin composition as described in [1], wherein above-mentioned (methyl) acrylic resin A's The difference of the glass transition temperature of glass transition temperature and above-mentioned (methyl) acrylic resin B is 20 DEG C or less.

[3] (methyl) acrylic resin composition as described in [1] or [2] is above-mentioned (methyl) acrylic acid series tree The melting mixing object of rouge A and above-mentioned (methyl) acrylic resin B.

[4] a kind of (methyl) acrylic resin film, it includes (methyl) acrylic acid described in any one of [1]~[3] Based resin composition.

[5] a kind of stretched film is made of stretching (methyl) acrylic resin film described in [4].

[6] a kind of polarization plates, it includes:

Polarizing coating and

Described in (methyl) acrylic resin film described in [4] that at least one side of above-mentioned polarizing coating is laminated or [5] Stretched film.

[7] polarization plates as described in [6], wherein be laminated with above-mentioned (methyl) acrylic acid series on one side in above-mentioned polarizing coating Resin film or above-mentioned stretched film are laminated with other transparent resin films in another side.

In accordance with the invention it is possible to provide the good toughness of display, thus operational (flexibility) good and heat shrink rate Small (methyl) acrylic resin film and its stretched film.In addition, in accordance with the invention it is possible to providing heat resistance high polarization plates.

Specific embodiment

< (methyl) acrylic resin composition >

(methyl) acrylic resin composition of the invention includes: a kind or 2 kinds of (methyl) acrylic resin A with (the first that upper and weight average molecular weight low with than being somebody's turn to do the glass transition temperature of (methyl) acrylic resin A is 100000 or more Base) acrylic resin B it is one kind or two or more.(methyl) acrylic resin composition according to the present invention, can improve As (flexibility) difference of poor toughness, thus operability the shortcomings that previous (methyl) acrylic resin film, and being capable of shape Good (methyl) acrylic resin film of small and heat resistance at heat shrink rate.

By the improvement of toughness, be able to suppress when (methyl) acrylic resin composition is filmed, to film after Film carry out the breakage of film that can be generated when stretch processing, notch, and be able to suppress the fragment that reason is damaged, notch generates The pollution of caused manufacturing process.In addition, by that will be received comprising the heating of (methyl) acrylic resin composition of the invention Small (methyl) acrylic resin film of shrinkage or its stretched film are used as the protective film for fitting in polarizing coating, can be improved polarization plates Heat resistance.

It should be noted that in the present invention, " (methyl) acrylic resin composition ", " (methyl) acrylic acid series tree " (methyl) acrylic acid " in rouge ", " (methyl) acrylic resin film " means methacrylic acid and/or acrylic acid, the point pair " (methyl) acrylic acid " in aftermentioned " (methyl) acrylic monomer " etc. is also the same.

(methyl) acrylic resin composition of the invention includes higher (methyl) acrylic acid of glass transition temperature It is Resin A and lower (methyl) the acrylic resin B of glass transition temperature.By the glass of (methyl) acrylic resin A Change transition temperature and is set as T_gA, the glass transition temperature of (methyl) acrylic resin B is set as T_gBWhen, preferably T_gAWith T_gBIt Difference (T_gA- T_gB) it is 20 DEG C or less.By by T_gA- T_gB20 DEG C are set as hereinafter, being easy to embody the above-mentioned effect (improvement of toughness With taking into account for the improvement of heat resistance).If T_gA- T_gBMore than 20 DEG C, then cannot obtain sufficient heat resistance sometimes, or with it is independent More deteriorated instead using heat resistance is compared when a kind of (methyl) acrylic resin.

It embodies above-mentioned effect from easy (improvement of the improvement and heat resistance of toughness takes into account), T_gA- T_gBIt is preferred that It is 3 DEG C or more, more preferably 7 DEG C or more, further preferably 10 DEG C or more.T_gA- T_gBWhen lower than 3 DEG C, use 2 kinds (methyl) The meaning of acrylic resin declines, and sufficient toughness cannot be obtained or cannot obtain sufficient heat resistance by having when film is made Tendency.

It is preferred that T_gAAnd T_gBRespectively according to T_gA- T_gBThe mode fallen within the above-described range is selected, from the improvement of toughness with From the perspective of the taking into account of the improvement of heat resistance, preferably according to T_gA- T_gBThe mode fallen within the above-described range is from 100 DEG C or more Range selects T_gA, T is selected from 80 DEG C or more of ranges_gB。T_gAAnd T_gBTypically respectively 150 DEG C hereinafter, preferably 140 DEG C or less.

Glass transition temperature T_gAAnd T_gBIt is measured according to JIS K7121:1987, it specifically, can be with aftermentioned The method recorded in the item of embodiment is measured.

The weight average molecular weight M of (methyl) acrylic resin A_wAIt is not particularly limited, such as can be 10000~ In the range of 1000000, but preferably 200000 or less.If M_wAMore than 1000000 or according to circumstances more than 200000, then The melt viscosity of (methyl) acrylic resin composition becomes excessively high, sometimes mixed with the melting of (methyl) acrylic resin B Refining becomes to be not easy to the forming of the film of (methyl) acrylic resin composition.

The weight average molecular weight M of (methyl) acrylic resin B_wB100000 or more are set as, thereby, it is possible to embody above-mentioned effect Fruit (taking into account for the improvement of the improvement and heat resistance of toughness).M_wBPreferably 120000 or more, more preferably 150000 or more.If M_wBLower than 100000, then the improvement of the toughness of (methyl) acrylic resin film obtained sometimes becomes inadequate, or with list It solely uses when a kind of (methyl) acrylic resin and more deteriorates instead compared to toughness.

In addition, M_wBIt can be for such as 1000000 hereinafter, but preferably 200000 or less.If M_wBMore than 1000000 or According to circumstances more than 200000, then the melt viscosity of (methyl) acrylic resin composition becomes excessively high, sometimes with (methyl) The melting mixing of acrylic resin A becomes to be not easy to the forming of the film of (methyl) acrylic resin composition.M_wB M can be more than or less than_wA, or can be with M_wAEqual extent (such as identical).

Weight average molecular weight M_wAAnd M_wBIt is using gel permeation chromatograph (GPC), by methacrylic resin (metering system Sour methyl esters) weight average molecular weight that finds out as standard sample specifically can use the side recorded in the item of aftermentioned embodiment Method is measured.

(methyl) acrylic resin A and B are the polymer comprising the Component units from (methyl) acrylic monomer. It is the polymer comprising methacrylate for (methyl) acrylic resin A and B typical case, preferably with methacrylate Based on, i.e. on the basis of total monomer amount comprising 50 weight % or more the Component units from methacrylate polymerization Object, the more preferably polymer of the Component units from methacrylate comprising 80 weight % or more.(methyl) acrylic acid It is Resin A and B can be the homopolymer of methacrylate respectively, is also possible on the basis of total monomer amount comprising 50 weight % The Component units from methacrylate and Component units of the 50 weight % or less from other polymerizable monomers are total to above Polymers.

As the above-mentioned methacrylate that can constitute (methyl) acrylic resin A and B, metering system can be used Acid alkyl ester, concrete example include methyl methacrylate, ethyl methacrylate, n propyl methacrylate, metering system Isopropyl propionate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid 2- ethyl The methacrylic acid that the carbon number of the alkyl of own ester, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate etc is 1~8 Arrcostab.The carbon number of alkyl is preferably 1~4.In (methyl) acrylic resin A and B, methacrylate can individually only With a kind, also two or more kinds may be used.

Wherein, from the viewpoint of heat resistance, preferably (methyl) acrylic resin A and B includes to come from methacrylic acid The Component units of methyl esters, comprising this composition unit of 50 weight % or more more preferably on the basis of total monomer amount, further preferably This composition unit comprising 80 weight % or more.

As the above-mentioned other polymerizable monomers that can constitute (methyl) acrylic resin A and B, it can be cited for example that third Polymerizable monomer other than olefin(e) acid ester, methacrylate and acrylate.As acrylate, acrylic acid alkyl can be used Ester, concrete example include methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, Isobutyl acrylate, tert-butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2- hydroxy methacrylate etc Alkyl carbon number be 1~8 alkyl acrylate.The carbon number of alkyl is preferably 1~4.In (methyl) acrylic resin A and In B, acrylate can be individually only with a kind, and also two or more kinds may be used.

As the polymerizable monomer other than methacrylate and acrylate, it can be cited for example that having 1 in the molecule The monofunctional monomer of the carbon-to-carbon double bond of a polymerism, the carbon-to-carbon double bond at least two polymerism is multifunctional in the molecule Monomer, but it is preferable to use monofunctional monomers.The concrete example of monofunctional monomer includes styrene, α-methylstyrene, vinyl first The styrenic monomers of benzene, halogenated styrenes etc；The alkenyl cyanogen of acrylonitrile, methacrylonitrile etc；Acrylic acid, metering system The unsaturated acids of acid, maleic anhydride etc；N- substituted maleimide amine.

In addition, the concrete example of polyfunctional monomer include ethylene glycol dimethacrylate, butanediol dimethylacrylate, The poly- esters of unsaturated carboxylic acids of the polyalcohol of trimethylolpropane trimethacrylate etc；Allyl acrylate, methacrylic acid alkene The alkenyl esters of the unsaturated carboxylic acid of propyl ester, allyl cinnamate etc；Diallyl phthalate, diallyl maleate, The virtue of the polyene base ester of the polyacid of triallylcyanurate, Triallyl isocyanurate etc, divinylbenzene etc Fragrant adoption alkenyl compound.Polymerizable monomer other than methacrylate and acrylate can be individually only with a kind, can also be with It is used in combination of two or more.

The preferred monomers of (methyl) acrylic resin A and B form the alkyl methacrylate on the basis of total monomer amount For 50~100 weight %, alkyl acrylate be 0~50 weight %, the polymerizable monomer other than these is 0~50 weight %, More preferable alkyl methacrylate is 50~99.9 weight %, alkyl acrylate is 0.1~50 weight %, other than these Polymerizable monomer is 0~49.9 weight %, and further preferred alkyl methacrylate is 80~99.9 weight %, alkyl acrylate Base ester is 0.1~20 weight %, the polymerizable monomer other than these is 0~19.9 weight %.

By making the monomer composition comprising above-mentioned etc monomer carry out free radical polymerization, (methyl) can be prepared respectively Acrylic resin A and B.Monomer composition can according to need comprising solvent, polymerization initiator.(methyl) acrylic resin The glass transition temperature T of A and B_gA、T_gBWith weight average molecular weight M_wA、M_wBCan by the type of monomer, each monomer content ratio, The adjustment of polymerizing condition, the degree of polymerization etc. controls.

In addition, the gimmick as the glass transition temperature for improving (methyl) acrylic resin, high molecular It is also effective that main chain, which imports ring structure,.Particularly preferred ring structure is cyclic acid anhydride structure, cyclic imide structure, lactone structure Equal heterocycle structures.Specifically, the cyclic acid anhydrides structures such as glutaric anhydride structure, succinic anhydride structure can be enumerated；Glutaryl is sub- The cyclic imides structures such as amine structure, succinimide structure；The lactones ring structure such as butyrolactone, valerolactone.Improve main chain In the content of ring structure then can more improve the glass transition temperature of (methyl) acrylic resin.Cyclic acid anhydride structure, ring Shape imide structure can import by the following method: by making maleic anhydride, maleimide etc. have the list of cyclic structure The method that body is copolymerized to import；The method for importing cyclic acid anhydride structure by dehydration-separating methanol condensation reaction after polymerization；Make ammonia Based compound reacts and the method etc. that imports cyclic imide structure.Resin (polymer) with lactone ring structure can pass through Following methods obtain: after the polymer on preparing macromolecular chain with hydroxyl and ester group, the hydroxyl in polymer that makes With ester group by heating, cyclizative condensation forms lactonic ring in the presence of the catalyst of organic phosphorus compound etc as needed The method of structure.

Polymer on macromolecular chain with hydroxyl and ester group for example can by by 2- (hydroxymethyl) methyl acrylate, 2- (hydroxymethyl) ethyl acrylate, 2- (hydroxymethyl) isopropyl acrylate, 2- (hydroxymethyl) n-butyl acrylate, 2- (methyl) acrylate with hydroxyl and ester group of (hydroxymethyl) tert-butyl acrylate etc be used as a part of monomer and It obtains.The more specific preparation method of polymer with lactone ring structure is recorded in such as Japanese Unexamined Patent Publication 2007-254726 Bulletin.

(methyl) of the invention as long as acrylic resin composition includes (methyl) acrylic resin A and (methyl) (methyl) acrylic resin A and (methyl) acrylic resin B (are combined by the resin combination of acrylic resin B Resin combination), then may include all forms, but in order to effectively obtain desired effect (improvement of toughness with it is resistance to Hot improvement takes into account), any one of form preferably below.

(a) consolidates after (methyl) acrylic resin A and (methyl) acrylic resin B melting mixing made of solidification The melting mixing object of body shape,

(b) is by the melting of liquid made of (methyl) acrylic resin A and (methyl) acrylic resin B melting mixing Mixture,

(c) is by (methyl) acrylic acid series of (methyl) the acrylic resin A and solid-like or liquid of solid-like or liquid The mixture that resin B mixes.

For typical case, microcosmic upper and (methyl) the acrylic resin A of the melting mixing object of above-mentioned (a) and (b) and (first Base) acrylic resin B mixing dispersion after melting mixing object.It should be noted that melting mixing object can be in the present invention Solid-like, or liquid.The melting mixing object of above-mentioned (a) can be the molding that forming is desired shape, It is also possible to non-shaped object.As the shape of molding, granular, graininess, membranaceous etc. can be enumerated.The melting of above-mentioned (b) is mixed Refining object is such as the liquid of (methyl) the acrylic resin composition prepared when forming film forming by heating Shape melting mixing object.

The mixture of above-mentioned (c) can be (methyl) acrylic resin of the solid-like of for example granular or graininess etc The mixture of (methyl) the acrylic resin B of the solid-like of A and granular or graininess etc, such mixture can become The raw material of the melting mixing object of above-mentioned (a) or (b).

In (methyl) acrylic resin composition of the invention, (methyl) acrylic resin A and (methyl) acrylic acid Be resin B content ratio with weight ratio meter, preferably 90/10~10/90, more preferably 80/20~20/80, further preferably It is 80/20~40/60.By the way that content ratio to be adjusted within the scope of this, capable of effectively obtaining desired effect, (toughness changes The kind improvement with heat resistance takes into account).If the content of (methyl) acrylic resin A is excessive, obtained (methyl) acrylic acid The toughness of resin film is easy to become inadequate.On the other hand, it if the content of (methyl) acrylic resin B is excessive, obtains The heat shrink rate of (methyl) acrylic resin film tend to get bigger.

(methyl) acrylic resin composition of the invention can according to need containing lubricant, fluorescent whitening agent, divide The addition such as powder, heat stabilizer, light stabilizer, ultraviolet absorbing agent, infrared absorbent, antistatic agent, antioxidant, solvent Agent it is one kind or two or more.

If can prevent will be comprising (methyl) acrylic acid series of (methyl) acrylic resin composition containing lubricant Rolling tightly when resin film is rolled into roll (volume I forms ま リ), it is coiled as a result, in the state of container dimensions (lotus appearance) improved. Lubricant is the lubricant with raising (methyl) acrylic resin film smoothness of the surface, such as has tristearin Sour based compound, (methyl) acrylic compounds, ester based compound etc..Wherein, stearic acid based compound can be preferably used as Lubricant.

The example of stearic acid based compound as lubricant other than stearic acid itself, further include methyl stearate, The stearate of ethyl stearte, glyceryl monostearate etc；Stearmide；Odium stearate, calcium stearate, zinc stearate, The Metallic stearates of lithium stearate, magnesium stearate etc；12- hydroxy stearic acid, 12- hydroxyl sodium stearate, 12- hydroxy stearate The 12- hydroxy stearic acid and its gold of sour zinc, 12- hydroxy stearic acid calcium, 12- hydroxy lithium stearate, 12- hydroxy stearic acid magnesium etc Belong to salt.Wherein it is possible to which it is preferable to use stearic acid.

Total 100 parts by weight of the use level of lubricant relative to (methyl) acrylic resin A and B, usually 0.15 Parts by weight hereinafter, preferably 0.1 parts by weight hereinafter, more preferably 0.07 parts by weight range below.If the use level of lubricant Excessively, then there is the risk that lubricant is oozed out by (methyl) acrylic resin film or reduced the transparency of film.

Ultraviolet absorbing agent is the compound that absorbing wavelength is 400nm ultraviolet light below.It will include (methyl) propylene When (methyl) acrylic resin film of sour based resin composition is used as the protective film of polarizing coating, by (methyl) acrylic acid series Cooperate ultraviolet absorbing agent in resin combination, can be improved the durable of the polarization plates for being fitted with the protective film on polarizing coating Property.That is, will not be made by making (methyl) acrylic resin film contain ultraviolet absorbing agent with the polarization plates of the film protective film Tone deteriorate and can effectively interdict ultraviolet light, be able to suppress be used for a long time polarization plates when degree of polarization reduce.

As ultraviolet absorbing agent, benzophenone series ultraviolet absorbing agent, enumerate BTA system ultraviolet radiation absorption can be used The well known ultraviolet absorbing agent of agent, acrylic ultraviolet absorbing agent etc.

The concrete example of ultraviolet absorbing agent includes 2,2 '-di-2-ethylhexylphosphine oxides (4- (1,1,3,3- tetramethyl butyl) -6- (2H- benzene And triazole -2- base) phenol), 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) -5- chlorobenzotriazole, the tertiary fourth of 2,4- bis- Base -6- (5- chlorobenzotriazole -2- base) phenol, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2,2 ', 4,4 '-four hydroxyls Base benzophenone.Wherein, 2,2 '-di-2-ethylhexylphosphine oxides (4- (1,1,3,3- tetramethyl butyl) -6- (2H- benzotriazole -2- base) benzene Phenol) it is one of preferred ultraviolet absorbing agent.

The use level of ultraviolet absorbing agent can be in (methyl) acrylic acid comprising (methyl) acrylic resin composition The wavelength 370nm light transmittance below of resin film is preferably 10% or less, more preferable 5% or less, further preferred 2% It is selected under conditions of range below.It is also preferable under wavelength 380nm according to (methyl) acrylic resin film Light transmittance is 25% or less, be further 15% or less, in particular 7% mode below cooperates ultraviolet absorbing agent.It is purple The use level of ultraviolet absorbers is in such a way that the light transmittance of (methyl) acrylic resin film meets condition shown here Appropriate adjustment.

Infrared absorbent is the compound of the infrared ray of absorbing wavelength 800nm or more, it can be cited for example that nitrosylation Close object or its metallic complex salt, cyanine based compound, side sour (squarylium) based compound, mercaptan nickel complex salt based compound, phthalein Cyanines based compound, naphthalene phthalocyanine based compound, triarylmethane based compound, imines (イ モ ニ ウ system) based compound, two Asias Amine compound, naphthoquinones based compound, anthraquinone based compound, amino-compound, ammonium salt based compound, carbon black, tin indium oxide, Antimony tin, the 4A race for belonging to periodic table, oxide, carbide or the boride of metal of 5A race or 6A race etc..These are infrared Light absorbers preferably select in the way of it can absorb whole infrared rays (light of the range of wavelength about 800~1100nm), can To be used in combination of two or more.The use level of infrared absorbent is preferably according to for example comprising (methyl) acrylic resin composition The light transmittance of the wavelength 800nm or more of (methyl) acrylic resin film is that 10% mode below is selected.

The opportunity containing additive in (methyl) acrylic resin composition is not particularly limited.Such as to this hair The case where bright (methyl) acrylic resin composition is filmed and makes the moldings such as (methyl) acrylic resin film Under, when (methyl) acrylic resin composition is the form of above-mentioned (a) the case where or to belong to the solid-like of above-mentioned (c) Mixture when, additive can be cooperated in the melting mixing object or mixture of the solid-like, then carry out melting mixing, It is filmed by melting extrusion etc..Alternatively, can be in the shape of the melting mixing object or above-mentioned (c) that prepare the form of above-mentioned (a) Cooperate additive in advance when the mixture of state.In addition, when (methyl) acrylic resin composition is the form of above-mentioned (b), Cooperate additive in the melting mixing object of liquid, is then filmed by melting extrusion etc..

< (methyl) acrylic resin film >

(methyl) acrylic resin film of the invention is (methyl) the acrylic resin combination comprising aforementioned present invention The film of object, typical case for, be the film being made of (methyl) acrylic resin composition of the invention.Due to (first of the invention Base) (methyl) the acrylic resin composition of acrylic resin film comprising aforementioned present invention, thus excellent tenacity, so behaviour Well, and heat shrink rate is small, excellent heat resistance for the property made (flexibility).(methyl) acrylic resin film can be by with one As film-forming method (methyl) acrylic resin composition of aforementioned present invention is filmed and is obtained.Wherein, it is preferred to use Melting extrusion is film-made method.

Melting extrusion film method typically refers to, and thermoplastic resin investment extruder is made its melting, is squeezed out by T mould membranaceous Molten resin is immediately directed against the method for being allowed to cool on chill roll and solidifying and continuously obtaining the film of long size.By suitably controlling The die lip gap etc. of T mould processed, can determine the thickness of film.The thickness of (methyl) acrylic resin film be usually 200 μm hereinafter, Preferably 40~150 μm.

(methyl) acrylic resin film can form the multilayer film of monofilm or two layers or more.In order to form multilayer film, Be typically employed in above-mentioned melting extrusion film method more extruders are set, by the molten resin of each extruder in T mould In in the way of becoming multilayer the coetrusion that squeezes out.In addition, can be enumerated as the other methods for being used to form multilayer film More extruders and T mould are continuously configured, the method by the membranaceous molten resin overlapping of extrusion to form multilayer film；It is making The method that membranaceous molten resin is overlapped on monofilm made of film to form multilayer film；Multiple single layers made of crimping film Method etc. of the film to form multilayer film.

When (methyl) acrylic resin film is multilayer film, each layer can be by (methyl) acrylic resin of same composition Composition is formed, and can also be formed by different (methyl) acrylic resin compositions formed.For example, it is also possible to as containing purple The stepped construction of the layer of ultraviolet absorbers and the layer without containing ultraviolet absorbing agent is such, and every layer of matching for change additive is combined At.

It is preferred that the center line average roughness at least one face of (methyl) acrylic resin film is 0.01~0.05 μm Left and right.When (methyl) acrylic resin film is used as the protective film of polarizing coating, preferably it is by the center line average roughness 0.01~0.05 μm or so of face is as the binding face with polarizing coating.Center line average roughness is advised according to JIS B 0601 The value of fixed method measurement.

If the center line average roughness on the surface of (methyl) acrylic resin film is lower than 0.01 μm, make film from figure Adhesion is easy to happen each other at film when rolling shape, and it is damaged that when extraction occurs film because of the mutual adhesion of film, thus grasps sometimes The property made is poor.In addition, if the center line average roughness on the surface of (methyl) acrylic resin film is more than 0.05 μm, with the face When being laminated on polarizing coating using adhesive layer, sufficient bonding force cannot be obtained sometimes, in addition, because film surface roughness caused by The scattering of reflected light becomes larger, and in the liquid crystal display device using obtained polarization plates, causes its picture albefaction or comparison sometimes The deterioration of the display quality of degree reduction etc.

The center line surface roughness of (methyl) acrylic resin film is adjusted to the method in above range without spy It does not limit, but for example in melting extrusion film method, since the surface transfer of its chill roll is to the film surface being in contact with it, Using the method for using the chill roll with the surface roughness in above range.

In addition, (methyl) acrylic resin film can be containing remaining molten in (methyl) acrylic resin A and/or B Agent, from the solvent of the solvent being added as needed in (methyl) acrylic resin composition etc., but (methyl) propylene Contained residual solvent amount is preferably 0.01 weight % or less on the basis of the weight of the film in sour resin film.Residual solvent amount can As weight reduced value when heating (methyl) acrylic resin film 30 minutes at 200 DEG C or as by being somebody's turn to do Heating and generate gas flow gas chromatography quantitative values and find out.

Even if by making 0.01 weight % of residual solvent amount hereinafter, being for example used as by (methyl) acrylic resin film In the case that the polarization plates of the protective film of polarizing coating are exposed under high temperature, high humidity environment, the deformation of protective film can be also prevented, and And the deterioration of the optical property of protective film and polarization plates can be prevented.

Residual solvent amount is that 0.01 weight % (methyl) acrylic resin film below can be for example, by following methods Obtain: the extruder that can be used in preparation (methyl) acrylic resin composition or can for film film when Ventilation hole is arranged in the suitable part of the extruder used, makes extruder inner pressure relief by the hole.

(methyl) acrylic resin film of the invention can have the surface-treated layer being laminated on the film.By right (methyl) acrylic resin film assigns surface-treated layer, can assign specific function according to the type of surface-treated layer. For the example of surface-treated layer, such as are as follows:

(a) be used for prevent surface abrasive hard conating,

(b) antistatic backing,

(c) anti-reflection layer,

(d) stain-proofing layer,

(e) undertakes that visibility improves, prevents the background of extraneous light from reflecting, interference based on prismatic lens and filter rubs The antiglare layer of your line (モ ア レ) reduction etc..

(hard conating)

Hard conating has the function of the surface hardness of raising (methyl) acrylic resin film, and the scratch for surface prevents The purpose of and be arranged.It is preferred that hard conating is in " general Shi test method (the coating ordinary test side of coating JIS K 5600-5-4:1999 Method)-the 5: engineering properties-Section 4 of film: scratch hardness (pencil method) " pencil hardness test of defined (will have hard The optical film of coating is placed on glass plate and is measured) in show H or the value harder than it.

Form the material that the material of hard conating is cured generally by heat, light.It can be cited for example that organic silicone system, The organic of melamine system, epoxy, acrylic acid series, urethane acrylate system etc hard applies material, silica etc Inorganic hard painting material.Wherein, good, productivity excellent, Ke Yiyou from the bonding force to (methyl) acrylic resin film Choosing applies material using urethane acrylate system or polyfunctional acrylic ester system firmly.

Hard conating according to expectation, for seek the adjustment of refractive index, the raising of bending elastic modulus, cubical contraction it is steady Fixedization, the purpose for the raising for further seeking heat resistance, static electricity resistance, anti-glare etc., can contain various fillers.In addition, Hard conating can also adding containing antioxidant, ultraviolet absorbing agent, light stabilizer, antistatic agent, levelling agent, defoaming agent etc Add agent.

(antistatic backing)

Shadow caused by antistatic backing assigns electric conductivity, inhibits because of electrostatic for the surface (methyl) acrylic resin film Ring the purpose of and be arranged.The formation of antistatic backing can be using the resin combination that will for example contain conductive material (antistatic agent) Object is coated on the method in (methyl) acrylic resin film.For example, passing through the hard painting in the formation for above-mentioned hard conating Antistatic agent coexists in advance in material, is capable of forming the hard conating of static electricity resistance.

(anti-reflection layer)

Anti-reflection layer is the layer for preventing the reflection of extraneous light, straight on the surface of (methyl) acrylic resin film It connects or is arranged across other layers such as hard conating.For (methyl) acrylic resin film with anti-reflection layer, preferably It is 2% hereinafter, more preferably for the light of wavelength 550nm for the reflectivity under 5 ° of incidence angle of the light of 430~700nm of wavelength Reflectivity under identical incidence angle is 1% or less.

The thickness of anti-reflection layer can be set to 0.01~1 μm or so, but preferably 0.02~0.5 μm.Anti-reflection layer can be with It is: comprising having the refractive index smaller than being provided with the refractive index of its layer ((methyl) acrylic resin film, hard conating etc.), tool There is the anti-reflection layer of the low-index layer of 1.30~1.45 refractive index for body；The low refraction of film comprising inorganic compound Rate layer and the film high refractive index layer comprising inorganic compound are alternately laminated the anti-reflection layer etc. of multilayer.

The material for forming above-mentioned low-index layer is then not particularly limited if the small material of refractive index.Example can be enumerated Such as the resin material of ultra-violet solidified (methyl) acrylic resin etc；Colloidal silicon dioxide etc is dispersed in resin The mixing material of inorganic particles；Sol-gel material etc. comprising alkoxy silane.Such low-index layer can pass through painting Polymer that cloth has polymerize and formed, can also be coated in the state of precursor monomer or oligomer, then make its polymerization It is solidified to form.In addition, in order to assign soil resistance, preferably comprising change in the molecule with fluorine atom for each material Close object.

As the sol-gel material for being used to form low-index layer, can properly use in the molecule has fluorine former The material of son.For typical example for the sol-gel material in the molecule with fluorine atom, there is Polyfluoroalkyl alkoxy Silane.Polyfluoroalkyl alkoxy silane can be such as following formula:

CF₃(CF₂)_nCH₂CH₂Si(OR)₃

Compound represented, herein, R indicate that the alkyl of carbon number 1~5, n indicate 0~12 integer.Wherein, preferably above-mentioned The compound that n in formula is 2~6.

As the concrete example of Polyfluoroalkyl alkoxy silane, compound below can be enumerated.

3,3,3- trifluoro propyl trimethoxy silane,

3,3,3- trifluoro propyl triethoxysilane,

Ten trifluoro octyl trimethoxy silane of 3,3,4,4,5,5,6,6,7,7,8,8,8-,

3,3,4,4,5,5,6,6,7,7,8,8,8- tridecafluoro-n-octyltriethoxysilane,

17 fluorine ruthenium trimethoxysilane of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-,

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- heptadecafluorodecyl triethoxysilane etc..

Low-index layer can also consolidating by thermosetting property fluorochemical or active energy ray-curable fluorochemical Compound is constituted.For the solidfied material, preferably its dynamic friction coefficient is in the range of 0.03~0.15, preferably with respect to water Contact angle is in the range of 90~120 °.As curable fluorine-containing compound, in addition to polyfluorinated alkyl silane compound (such as Above-mentioned 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- heptadecafluorodecyl triethoxysilanes etc.) except, may be used also To enumerate the fluoropolymer with cross-linking functional group.

Fluoropolymer with cross-linking functional group can manufacture by the following method: 1) making fluorochemical monomer and have friendship The method of the monomer copolymerization of Lian Xing functional group is copolymerized fluorochemical monomer with the monomer with functional group, then to polymer In above-mentioned functional group's addition have cross-linking functional group compound method.

As above-mentioned fluorochemical monomer, it can be cited for example that vinyl fluoride, vinylidene fluoride, tetrafluoroethene, hexafluoropropene, complete The fluoroolefins class of fluoro- 2,2- dimethyl -1,3- dioxole etc；The partly or completely perfluoroalkyl of (methyl) acrylic acid Ester derivant class；The complete or partial fluorovinylether class of (methyl) acrylic acid.

As the monomer with above-mentioned cross-linking functional group or with the compound of cross-linking functional group, it can be cited for example that The monomer with glycidyl of glycidyl acrylate, glycidyl methacrylate etc；Acrylic acid, methyl-prop The monomer with carboxyl of olefin(e) acid etc；The list with hydroxyl of dihydroxypropyl alkyl ester, methacrylic acid hydroxyl alkyl ester etc Body；The monomer with alkenyl of allyl acrylate, allyl methacrylate etc；Monomer with amino；With sulfonic acid The monomer of base.

From can be improved marresistance, be used to form low-index layer material can also by comprising silica, The material that the inorganic compounds particle such as aluminium oxide, titanium dioxide, zirconium oxide, magnesium fluoride is scattered in the colloidal sol in alcoholic solvent is constituted. For used inorganic compound particle from the viewpoint of antireflection, refractive index is smaller the more preferred thus.The inorganic compound Particle can have gap, the hollow minute particle of particularly preferred silica.The average grain diameter of hollow minute particle is preferably in 5~2000nm In the range of, especially more preferably in the range of 20~100nm.Average grain diameter described herein is to utilize transmission electron microscope Observe the number average bead diameter acquired.

(stain-proofing layer)

Stain-proofing layer is arranged to assign waterproofness, grease proofness, absorption of perspiration, soil resistance etc..It is used to form the suitable of stain-proofing layer Suitable material is fluorinated organic compound.As fluorinated organic compound, can enumerate fluorocarbon, perfluor silane, they High-molecular compound etc..The forming method of stain-proofing layer can be according to the material of formation, using to be deposited, be sputtered to typical example Physical vaporous deposition, chemical vapour deposition technique, wet coating method etc..The average thickness of stain-proofing layer is usually 1~50nm or so, Preferably 3~35nm.

(antiglare layer)

Antiglare layer be surface have subtle concaveconvex shape layer, it is preferable to use above-mentioned hard painting material and formed.

There is the antiglare layer of subtle concaveconvex shape can be formed by the following method on surface: 1) being formed in (methyl) propylene Contain fine-grained film on sour resin film, the concave-convex method based on the particle is set；2) in (methyl) acrylic resin After forming the film for containing or not contain particle on film, the metal die (roller etc.) to surface with concaveconvex shape is pushed to transfer Method (also referred to as embossing) of concaveconvex shape etc..

In above-mentioned method 1), the hardening resin composition comprising curability transparent resin and particle is coated on In (methyl) acrylic resin film, and solidify coating layer by the irradiation of the light such as ultraviolet light or heating, it is anti-so as to be formed Dizzy layer.Preferred consolidation transparent resin is selected from the material of high rigidity (hard to apply).It, can be with as the curability transparent resin Using the light-cured resin of uv curing resin etc, thermosetting resin, electron ray curing resin etc., but from life Yield, obtained antiglare layer the viewpoints such as hardness set out, it is preferable to use light-cured resin, more preferably ultra-violet solidified tree Rouge.When using light-cured resin, hardening resin composition also includes Photoepolymerizationinitiater initiater.

As light-cured resin, multifunctional (methyl) acrylate is generally used.Its concrete example includes trihydroxy methyl third The two-of alkane or three-(methyl) acrylate；The three-of pentaerythrite or four-(methyl) acrylate；At least have 1 in the molecule (methyl) acrylate of a hydroxyl and reaction product, that is, polyfunctional carbamate (methyl) acrylic acid of diisocyanate Ester.These multifunctional (methyl) acrylates can use individually, or two or more is applied in combination as needed.

Furthermore it is also possible to by polyfunctional carbamate (methyl) acrylate, polyalcohol (methyl) acrylate and The mixture of (methyl) acrylate copolymer with the alkyl comprising 2 or more hydroxyls is as light-cured resin.Constituting should Polyfunctional carbamate (methyl) acrylate of light-cured resin uses such as (methyl) acrylic acid and/or (methyl) third Olefin(e) acid ester, polyalcohol and diisocyanate manufacture.Specifically, by by (methyl) acrylic acid and/or (methyl) propylene Acid esters and polyols preparation have hydroxyl (methyl) acrylate of at least one hydroxyl in the molecule, make itself and diisocyanate Reaction, thus, it is possible to manufacture polyfunctional carbamate (methyl) acrylate.Thus polyfunctional carbamate (the first manufactured Base) acrylate become before the light-cured resin itself enumerated.In its manufacture, (methyl) acrylic acid and/or (methyl) Acrylate can be used singly, or in combination of two or more kinds respectively, and polyalcohol and diisocyanate are also the same, Ke Yifen It is not used singly, or in combination of two or more kinds.

A kind of (methyl) acrylate of raw material as polyfunctional carbamate (methyl) acrylate can be (first Base) acrylic acid chain or cyclic alkyl ester.As its concrete example, (methyl) methyl acrylate, (methyl) propylene can be enumerated (methyl) acrylic acid of acetoacetic ester, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate etc (methyl) acrylate base ester of Arrcostab and (methyl) cyclohexyl acrylate etc.

The polyalcohol of another raw material as polyfunctional carbamate (methyl) acrylate is that have in the molecule The compound of at least two hydroxyl.It can be cited for example that ethylene glycol, propylene glycol, 1,3- propylene glycol, diethylene glycol, dipropylene glycol, new Pentanediol, 1,3 butylene glycol, 1,4- butanediol, 1,6-HD, 1,9- nonanediol, 1,10- decanediol, 2,2,4- trimethyl- 1,3- pentanediol, 3- methyl-1,5- pentanediol, the neopentyl glycol ester of 3-hydroxypivalic acid, cyclohexanedimethanol, 1,4- hexamethylene two Alcohol, the spiroglycol, Tricyclodecane Dimethanol, hydrogenated bisphenol A, oxireme addition bisphenol-A, propylene oxide addition bisphenol-A, three hydroxyls Methyl ethane, trimethylolpropane, glycerol, 3- methylpentane -1,3,5- triol, pentaerythrite, dipentaerythritol, three seasons penta 4 Alcohol, glucose etc..

The diisocyanate of still another raw material as polyfunctional carbamate (methyl) acrylate is in molecule Inside there is the compound of 2 isocyanate group (- NCO), the various diisocyanates of aromatic series, aliphatic or ester ring type can be used Ester.As concrete example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate can be enumerated Ester, 2,4- tolylene diisocyanate, 4,4 '-diphenyl diisocyanates, 1,5- naphthalene diisocyanate, 3,3 '-dimethyl -4, 4 '-diphenyl diisocyanates, xylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4 '-diphenyl methanes Diisocyanate and the nuclear hydrogenation object of diisocyanate etc. wherein with aromatic rings.

Polyalcohol (the first of above-mentioned light-cured resin is constituted together with polyfunctional carbamate (methyl) acrylate Base) acrylate be in the molecule at least two hydroxyl compound (i.e. polyalcohol) (methyl) acrylate.As it Concrete example can enumerate pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate etc..Polyalcohol (methyl) acrylate can be individually only with a kind, and also two or more kinds may be used.Polyalcohol (methyl) acrylate preferably includes Pentaerythritol triacrylate and/or pentaerythritol tetraacrylate.

In turn, the structure together with these polyfunctional carbamate (methyl) acrylate and polyalcohol (methyl) acrylate (methyl) acrylate copolymer at light-cured resin, with the alkyl comprising 2 or more hydroxyls is single in a composition With the polymer of the alkyl comprising 2 or more hydroxyls in member.It can be cited for example that including (methyl) acrylic acid 2,3- dihydroxy Propyl ester as the polymer of Component units, together with (methyl) acrylic acid 2,3- dihydroxy propyl ester also include (methyl) acrylic acid 2- Polymer etc. of the hydroxy methacrylate as Component units.

More than, by using the light-cured resin of (methyl) acrylic acid series as illustration, can obtain and (methyl) The adaptation of acrylic resin film improves and mechanical strength raising, the antiglare film that can effectively prevent surface injury.

As above-mentioned particle, it is preferable to use average grain diameter be 0.5~5 μm and with the curability transparent resin after solidification The particle that refringence is 0.02~0.2.It, can be effective by using the particle of average grain diameter and refringence in the range Embody turbidity.The average grain diameter of the particle can be acquired by dynamic light scattering method etc..Average grain diameter at this time is weight average particle diameter.

Particle can be organic fine particles or inorganic particles.As organic fine particles, resin particle is generally used, example can be enumerated Such as it is crosslinked poly- (methyl) acrylic particles, methyl methacrylate/styrene copolymer resin particle, crosslinked polystyrene grain Son, crosslinked polymethylmethacrylaparticles particle, silicone resin particle, polyimide particle etc..In addition, as inorganic particles, it can To use silica, colloidal silicon dioxide, aluminium oxide, alumina sol, aluminosilicate, alumina silica composite oxygen Compound, kaolin, talcum, mica, calcium carbonate, calcium phosphate etc..

As above-mentioned Photoepolymerizationinitiater initiater, acetophenone system, benzophenone series, benzoin ether system, amine system, oxidation can be used The various substances such as phosphine system.The example for being classified as the compound of acetophenone system Photoepolymerizationinitiater initiater includes 2,2- dimethoxy -2- Phenyl acetophenone (alias dibenzoyl dimethyl ketal), 2,2- diethoxy acetophenone, 1- (4- isopropyl phenyl) -2- hydroxyl - 2- methylpropane -1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl -2- morpholino base -1- (4- methyl thio phenyl) propane -1- Ketone.The example for being classified as the compound of benzophenone series Photoepolymerizationinitiater initiater includes benzophenone, 4- chlorobenzophenone, 4, 4 '-dimethoxy-benzophenones.The example for being classified as the compound of benzoin ether system Photoepolymerizationinitiater initiater includes benzoin first Base ether, benzoin propyl ether.The example for being classified as the compound of amine system Photoepolymerizationinitiater initiater includes N, N, N ', N '-tetramethyl- 4,4 '-diaminobenzophenones (alias Michler's keton).The example of phosphine oxide system Photoepolymerizationinitiater initiater includes 2,4,6- trimethylbenzene Formoxyl diphenyl phosphine oxide.In addition to this, it is poly- to can also be used as light for xanthone based compound, thioxanthone based compound etc. Initiator is closed to use.

These Photoepolymerizationinitiater initiaters are in market sale.If enumerating the example of representative commercially available product with trade name, have by " Irgacure 907 ", " Irgacure 184 ", " the Lucirin TPO " etc. that BASF AG of Germany sells.

Hardening resin composition can according to need comprising solvent.As solvent, such as ethyl acetate, vinegar can be used Acid butyl ester etc, can dissolve constitute hardening resin composition each ingredient arbitrary organic solvent.It can also mix Use organic solvent of more than two kinds.

In addition, hardening resin composition can contain levelling agent, the levelling agent of such as fluorine system or silicone-based can be used. The levelling agent of silicone-based has reactive silicone, dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, poly- methyl alkyl silicon Oxygen alkane etc..Reactive silicone and siloxane-based levelling agent are preferably in silicone-based levelling agent.If using reactive silicon is included The levelling agent of ketone, then anti-glare layer surface is endowed slickness, and excellent marresistance can be made to continue for a long time.In addition, if using Siloxane-based levelling agent can be improved film formability.

On the other hand, when forming the antiglare layer with fine surface concaveconvex shape using above-mentioned method (embossing) 2), Using the mold for being formed with fine irregularities shape, by the shape transfer of mold to being formed in (methyl) acrylic resin film Resin layer.When forming fine surface concaveconvex shape by embossing, the resin layer for transferring concaveconvex shape can contain particle, Particle can also not contained.Constitute above-mentioned resin layer resin be preferably in above-mentioned method 1) illustrate as photo-curable Resin, more preferably uv curing resin.But by proper choice of Photoepolymerizationinitiater initiater, can also using can with than The longer visible light of the wavelength of ultraviolet light carries out cured visible-light curing resin and replaces uv curing resin.

In embossing, it will be coated with comprising the hardening resin composition of the light-cured resins such as uv curing resin In (methyl) acrylic resin film, solidify when pushing its coating layer to the male and fomale(M&F) of mold, thus mold Male and fomale(M&F) is transferred to coating layer.More specifically, hardening resin composition is coated on (methyl) acrylic resin film On, in the state of making coating layer be sealed at the male and fomale(M&F) of mold, by (methyl) acrylic resin film side irradiation ultraviolet light etc. Light and solidify coating layer, then, will have solidify after coating layer (antiglare layer) (methyl) acrylic resin film by mould Tool removing, so that the concaveconvex shape of mold is needed on antiglare layer.

The thickness of antiglare layer is not particularly limited, but generally 2~30 μm, preferably 3 μm or more, and preferably 20 μm Below.If antiglare layer is excessively thin, presence cannot obtain sufficient hardness, surface becomes easy injured tendency, on the other hand, if Antiglare layer is blocked up, then exists and be easy that damaged or what productivity reduced due to the cure shrinkage of antiglare layer makes film that curling occur inclines To.

It is preferred that the turbidity value of (methyl) acrylic resin film with antiglare layer is in the range of 5~50%.If turbidity It is worth too small, then cannot obtains sufficient anti-dazzle performance, will be provided with the polarization plates of (methyl) acrylic resin film with antiglare layer The background reflection of extraneous light is easy to produce when applied to image display device in picture.On the other hand, if the turbidity value is excessive, Although then can reduce the background reflection of extraneous light, the contrast (ま り) of the picture of black display is reduced.Turbidity value is Ratio of the diffused transmission rate relative to total light transmittance, according to JIS K 7136:2000 " プ ラ ス チ ッ Network-transparent material ヘ ー ズ asks the side め (the seeking method of plastics-transparent material turbidity) " it is measured.

< stretched film >

Stretched film of the invention is to carry out aforementioned present invention (methyl) acrylic resin film made of stretch processing Film.Since stretched film of the invention also includes (methyl) acrylic resin composition of aforementioned present invention, excellent tenacity, So operational (flexibility) is well, and heat shrink rate is small and excellent heat resistance.

As stretch processing, it can enumerate and be uniaxially stretched, is biaxial stretch-formed etc..As draw direction, can enumerate non-stretched Mechanical (MD), orthogonal to that direction (TD) and the machinery of flowing to of film flows to direction of (MD) oblique etc..It is biaxial stretch-formed to can be It is biaxial stretch-formed while stretching simultaneously along 2 draw directions, it is also possible to stretch in another direction after stretching along prescribed direction It is gradually biaxial stretch-formed.

Stretch processing can be by using increasing 2 pairs or more of niproll of the peripheral speed of outlet side, along length It spends direction (machinery flow direction: MD) to stretch, or holds on the two side ends of unstretching film and orthogonal along flowing to machinery with chuck Direction (TD) extends to carry out.

Stretching ratio based on stretch processing is preferably more than 0~500%, more preferably 100~300%.If stretching again Rate is more than 300%, then film thickness becomes too thin and becomes easy fracture, and operability reduces.Stretching ratio can be asked by following formula Out:

Stretching ratio (%)=100 × { (length after stretching)-(length before stretching) }/(length before stretching).

Draft temperature be set as (methyl) acrylic resin film integrally can be carried out stretching degree show mobility More than temperature, preferably in the range of -40 DEG C to+40 DEG C of the glass transition temperature of (methyl) acrylic resin film, more In the range of preferably -25 DEG C to+25 DEG C, in the range of further preferably -15 DEG C to+15 DEG C.

The thickness of stretched film is usually 100 μm hereinafter, preferably 10~80 μm.

< polarization plates >

Polarization plates of the invention include polarizing coating and the polarizing coating at least one side be laminated aforementioned present invention (first Base) acrylic resin film or aforementioned present invention stretched film.(methyl) acrylic resin film and stretched film can be protection The protective film of polarizing coating.In polarization plates of the invention, (methyl) propylene of the invention can be laminated on the two sides of polarizing coating Sour resin film or stretched film can also be laminated with (methyl) acrylic resin film or drawing of the invention in polarizing coating on one side Film is stretched, another side is laminated with other transparent resin films as protective film or phase difference film.These (methyl) acrylic resins Film, stretched film, transparent resin film can be used bonding agent with polarizing coating and be bonded.

(polarizing coating)

Polarizing coating according to known methods, can be manufactured by following process: polyvinyl alcohol resin film be carried out uniaxial The process of stretching；By carrying out dyeing to polyvinyl alcohol resin film with dichroism pigment to adsorb the work of the dichroism pigment Sequence；The process for being adsorbed with the polyvinyl alcohol resin film of dichroism pigment is handled with boric acid aqueous solution；And utilizing boric acid water The process washed after the processing of solution.Thus polarizing coating obtained by, which becomes to have on the above-mentioned direction being uniaxially stretched, to be inhaled Receive the polarizing coating of axis.

As polyvinyl alcohol resin, can be used the resin after the saponification of polyvinyl acetate system resin.As poly-vinegar Vinyl acetate system resin can also enumerate acetic acid second other than as the polyvinyl acetate of the homopolymer of vinylacetate The copolymer etc. of enester and the other monomers that can be copolymerized with it.It, can as can be with vinyl acetate copolymerized other monomers To enumerate such as unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, (methyl) acryloyl with ammonium Amine etc..

The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of %, preferably 98 moles of % or more.Polyvinyl alcohol It is that resin can be modified, can be used such as with the modified polyvinyl formal of aldehydes, polyvinyl acetal. In addition, the degree of polymerization of polyvinyl alcohol resin is usually 1000~10000 or so, preferably 1500~5000 or so.

Film after such polyvinyl alcohol resin is filmed is used as the former material film of polarizing coating.By polyethenol series The method that resin is filmed is not particularly limited, using well known method.The film thickness of polyethenol series former material film is not special Limitation, for example, 10~150 μm or so.

Polyvinyl alcohol resin film be uniaxially stretched can using dichroism pigment dyeing before, with dyeing simultaneously or It carries out after dyeing.In the case where being uniaxially stretched after dyeing, this is uniaxially stretched can be before boric acid processing or at boric acid It is carried out in reason.Alternatively, it is also possible to be uniaxially stretched in these stages.

Be uniaxially stretched can be by carrying out between the different isolated roller of peripheral speed, can also be by being pressed from both sides with hot-rolling It holds to carry out.In addition, this, which is uniaxially stretched, can be the dry type stretching stretched in air, be also possible to using water, have Solvent equal solvent makes the wet tensile stretched in the state of polyvinyl alcohol resin membrane swelling.Stretching ratio is usually 3 ~8 times or so.

Polyvinyl alcohol resin film can be for example, by containing dichroism pigment using the dyeing of dichroism pigment The method of polyvinyl alcohol resin film is impregnated in aqueous solution to carry out.As dichroism pigment, it is organic that iodine, dichroism can be used Dyestuff.It should be noted that it is preferred that polyvinyl alcohol resin film implements impregnation in water before carrying out dyeing processing.

When using iodine as dichroism pigment, it is typically employed in the aqueous solution containing iodine and potassium iodide and impregnates polyethylene The method that alcohol resin film is dyed.The content of iodine in the aqueous solution in the water of every 100 parts by weight, usually 0.01~ 1 parts by weight or so.The content of potassium iodide is in the water of every 100 parts by weight, usually 0.5~20 parts by weight or so.For dyeing The temperature of aqueous solution be usually 20~40 DEG C or so.In addition, to the dip time (dyeing time) of the aqueous solution be usually 20 ~1800 seconds or so.

On the other hand, it as dichroism pigment when using dichroic organic dye, is typically employed in comprising water-soluble The method that polyvinyl alcohol resin film is dyed is impregnated in the aqueous solution of dichroic organic dye.Dichroism in the aqueous solution The content of organic dyestuff is in the water of every 100 parts by weight, and usually 1 × 10^-4~10 parts by weight or so, preferably 1 × 10^-3~1 Parts by weight or so.The aqueous solution can contain the inorganic salts such as sodium sulphate as dyeing assistant.Dichroic dye water for dyeing The temperature of solution is usually 20~80 DEG C or so.In addition, the dip time (dyeing time) into the aqueous solution be usually 10~ 1800 seconds or so.

It can be soaked by the polyvinyl alcohol resin film after dyeing using the boric acid processing after the dyeing of dichroism pigment Method of the stain in boracic aqueous acid carries out.The content of boric acid in boracic aqueous acid in the water of every 100 parts by weight, Usually 2~15 parts by weight or so, preferably 5~12 parts by weight.When using iodine as dichroism pigment, the preferred boracic sour water Solution contains potassium iodide.The content of potassium iodide in boracic aqueous acid is in the water of every 100 parts by weight, and usually 0.1~15 Parts by weight or so, preferably 5~12 parts by weight.Dip time into boracic aqueous acid is usually 60~1200 seconds or so, Preferably 150~600 seconds, further preferably 200~400 seconds.The temperature of boracic aqueous acid is usually 50 DEG C or more, preferably It is 50~85 DEG C, further preferably 60~80 DEG C.

Treated that polyvinyl alcohol resin film usually carries out washing process for boric acid.Washing process is for example by will be at boric acid Polyvinyl alcohol resin film immersion after reason carries out in water.The temperature of water in washing process is usually 5~40 DEG C or so. In addition, dip time is usually 1~120 second or so.

Implement to be dried after washing, obtains polarizing coating.Air drier, FAR INFRARED HEATING can be used in drying process Device carries out.The temperature of drying process is usually 30~100 DEG C or so, and preferably 50~80 DEG C.The time of drying process is usual It is 60~600 seconds or so, preferably 120~600 seconds.

By being dried, the moisture rate of polarizing coating is reduced to practical level.Its moisture rate is usually 5~20 weights Measure %, preferably 8~15 weight %.If moisture rate is lower than 5 weight %, the flexible of polarizing coating is lost sometimes, and polarizing coating is at it Damage or fracture occur after drying.On the other hand, if moisture rate is more than 20 weight %, there are the thermal stability of polarizing coating not The tendency of foot.

The thickness that can make the polarizing coating of thus obtained dichroism pigment gas absorption quantity is usually 5~40 μm or so.

(transparent resin film)

As set forth above, it is possible in polarizing coating be fitted with (methyl) acrylic resin film or stretched film of the invention Face opposite side face on, be bonded other transparent resin films.Transparent resin film can be the protective film or phase difference film of polarization plates.

Transparent resin film can be for example tri acetyl cellulose membrane, polycarbonate membrane, polyethylene terephthalate film, (methyl) acrylic resin film, the stacked film of (methyl) acrylic resin layer and polycarbonate-based resin layer, olefin-based tree Adipose membrane etc..Wherein it is possible to which it is preferable to use olefin-based resin films.

Olefin-based resin refers to, such as makes the chain olefin monomer or drop of ethylene, propylene etc using catalyst for polymerization Resin obtained from the cyclic olefin monomers polymerization of bornylene and cyclopentadiene derivant etc.

As the olefin-based resin obtained by chain olefin monomer, polyethylene-based resin, polypropylene-based resin can be enumerated. Wherein, preferred homopolymer, that is, polypropylene-based resin of propylene.It is also preferable to based on propylene, usually with 1~20 weight % Ratio, be preferably copolymerized with the enabled comonomer being copolymerized with it of the ratio of 3~10 weight % made of polypropylene-based copolymerization Resin.

As the comonomer that can be copolymerized with propylene, optimal ethylene, 1- butylene or 1- hexene.Wherein, from the transparency, drawing Stretch that processability is more excellent to set out, it is preferable to use ethylene, is total to ethylene with 1~20 weight %, especially with the ratio of 3~10 weight % Polypropylene-based copolymer resins after poly- are one of preferred substances.By the way that the copolymerization ratios of ethylene are set as 1 weight % or more, occur Improve the transparency, the effect of stretch process.On the other hand, if its ratio is more than 20 weight %, the fusing point of resin drops sometimes Low, heat resistance required by protective film or phase difference film is impaired.

The commercially available product of polypropylene-based resin can be readily available, such as respectively for trade name, can enumerate by Prime Polymer Co., " Prime Polypro " that Ltd is sold, by Japan Polypropylene Corporation " NOVATEC " and " WINTEC " that sells, " the SUMITOMO NOBLEN " sold by Sumitomo Chemical Co, by Sun Aroma Co., " the SUN AROMA " etc. that Ltd is sold.

The olefin-based resin for making cyclic olefin monomers be polymerized is also commonly referred to as annular ethylene series resin, ester ring type alkene It is resin or norbornene resin.Referred to here as annular ethylene series resin.

As annular ethylene series resin, it can be cited for example that: to pass through diels A De by cyclopentadiene and olefines Norbornene that ear reaction obtains or derivatives thereof carries out ring opening metathesis polymerization for monomer, then by adding tree obtained by hydrogen Rouge；With the Fourth Ring ten obtained by bicyclopentadiene and olefines or (methyl) esters of acrylic acid by Diels-Alder reaction Two carbenes or derivatives thereof are that monomer carries out ring opening metathesis polymerization, then by adding resin obtained by hydrogen；Using norbornene, Two or more in tetracyclododecane, their derivative species or other cyclic olefin monomers is carried out similarly ring-opening methathesis Copolymerization, then by adding resin obtained by hydrogen；Make in above-mentioned norbornene, tetracyclododecane and their derivative At least one kind of cyclic olefin and resin obtained by the aliphatic or aromatic compound addition polymerization with vinyl etc..

The commercially available product of annular ethylene series resin can also be readily available, such as respectively for trade name, can be enumerated By the TOPAS ADVANCED POLYMERS GmbH production of Germany, in Japan by Polyplastics Co., what Ltd was sold " TOPAS ", by JSR Corp.'s manufacture, " ARTON " that sells, by Japanese Zeon Corporation manufacture, sell " ZEONOR " and " ZEONEX ", by Mitsui Chemicals, Inc's manufacture, " APEL " that sells etc..

It is filmed and membranization, can be formed in partially by by above-mentioned chain olefin system resin or annular ethylene series resin The transparent resin film of the one side fitting of vibrating diaphragm.The method of membranization is not particularly limited, and preferably can be film-made method using melting extrusion.

The commercially available product of olefin-based resin film can also be readily available, such as if polypropylene-based resin film, then respectively For trade name, " the FILMAX CPP FILM " sold by FILMAX company can be enumerated, by Suntox Co., what Ltd was sold " SUNTOX ", " TOHCELLO " that is sold by Tohcello, the Inc., " TOYOBO sold by Toyo Boseki K.K PYLEN FILM ", Toray Advanced Film Co., Ltd (eastern レ Off ィ Le system processes Co., Ltd.) are sold " ニ ホ Application Port リ エ ー ス ", the Futamura Chemical that " TORAYFAN ", Port リ エ ー ス Co., Ltd. of Japan sell Co., " too pavilion FC " etc. that Ltd is sold.In addition, respectively for trade name, can be enumerated day if annular ethylene series resin film " the ARTON FILM " etc. that " ZEONOR FILM " that this Zeon Corporation is sold, JSR Corp. sell.

For transparent resin film, optical functional film or coated optical functional layer can also be laminated on its surface.As this The optical functional film and optical functional layer of sample, it can be cited for example that adhesive layer, conductive layer, hard conating etc..

By making olefin-based resin film stretching described above film that there is refractive anisotrop, a phase can be assigned The function of poor film.Drawing process is suitably selected according to required refractive anisotrop, is not particularly limited, using for example Vertical single ax stretches, horizontal is uniaxially stretched or gradually biaxial stretch-formed in length and breadth.

Olefin-based resin has positive refractive anisotrop, and refractive index is maximum on the direction for applying stress, therefore its The film being uniaxially stretched generally gives to n_x> n_y≈n_zRefractive anisotrop.Herein, n_xFor phase axis direction slow in the face of film (in face the maximum direction of refractive index, resin with positive refractive anisotrop draw direction) refractive index, n_yFor The refractive index in leading phase shaft direction (direction orthogonal with slow phase axis in face), n in the face of film_zFor the refraction of the normal direction of film Rate.Olefin-based resin generally gives to n by gradually biaxial stretch-formed film_x> n_y> n_zRefractive anisotrop.

In addition, in order to assign desired refractive index characteristic, it can also be by being fitted in heat-shrinkable film as target Film on, the method for shrinking film instead of stretch process or while stretch process manufactures phase difference film.The operation is usual It is that refractive anisotrop is n in order to obtain_x> n_z> n_yOr n_z> n_x≥n_yPhase difference film and carry out.

The commercially available product of phase difference film comprising olefin-based resin can also be readily available.For example, if cyclic annular alkene is included The phase difference film of hydrocarbon system resin can enumerate " the ZEONOR sold by Japanese Zeon Corporation then for trade name FILM ", " the ARTON FILM " that is sold by JSR Corp., " the ESSINA phases sold by Sekisui Chemical Co., Ltd Poor film " etc..

(bonding agent)

For being bonded of (methyl) acrylic resin film or stretched film and polarizing coating, the patch of polarizing coating and transparent resin film It closes, uses bonding agent as described above.It is preferred that before fitting, in (methyl) acrylic resin film or stretched film with polarization In the binding face and polarizing coating of film in the binding face of (methyl) acrylic resin film or stretched film at least one party and At least one party in the binding face with polarizing coating in the binding face and transparent resin film with transparent resin film in polarizing coating, in advance First implement Corona discharge Treatment, plasma irradiating processing, electronbeam irradiation processing, the processing of other surface activations.

Bonding agent for fitting can be from the bonding agent for showing bonding force to the membrane body being bonded, and arbitrarily selection comes It uses.For typical case, water system bonding agent can be enumerated, that is, dissolve bonding agent ingredient in water or make bonding agent ingredient in water The bonding agent of middle dispersion, the active energy ray-curable bonding comprising the cured ingredient of irradiation by active energy beam Agent.It is preferable to use active energy ray-curable bonding agents from the viewpoint of productivity.

Firstly, if being illustrated to water system bonding agent, it can be cited for example that using polyvinyl alcohol resin, polyurethane tree Rouge makees composition as main component as preferred bonding agent.

When using polyvinyl alcohol resin as the main component of water system bonding agent, the polyvinyl alcohol resin is in addition to part Except saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl modified poly- second can also be The polyvinyl alcohol resin of the modification of enol, methylol-modified polyvinyl alcohol, amino modified polyvinyl alcohol etc.Use polyethylene When alcohol system resin is as bonding agent ingredient, which is prepared into the aqueous solution of polyvinyl alcohol resin mostly.Bonding agent is water-soluble Water of the concentration of polyvinyl alcohol resin in liquid relative to 100 parts by weight, usually 1~10 parts by weight or so, preferably 1~ 5 parts by weight.

For to improve cementability, preferably adding second with polyvinyl alcohol resin water system bonding agent as main component The curability composition or crosslinking agent of dialdehyde, water-soluble epoxy resin etc.As water-soluble epoxy resin, it can be cited for example that: Make poly- by the polyalkylenepolyamines of two sub- second triamines, tetramine etc and reacting for the dicarboxylic acids of adipic acid etc Polyamide-polyamino, reacted with epichlorohydrin obtained by polyamide polyamines epoxy resin.City as the polyamide polyamines epoxy resin Sell product, have " the Sumirez Resin 650 " and " Sumirez Resin675 " for example sold by field ridge chemical industry (strain), by " WS-525 " etc. that Japan PMC Corp sells, can be suitably used these.These curability compositions or crosslinking agent add Dosage is relative to 100 parts by weight of polyvinyl alcohol resin, usually 1~100 parts by weight, preferably 1~50 parts by weight.If it adds Dosage is few, then cementability improvement effect becomes smaller, and on the other hand, if its additive amount is more, adhesive layer has the tendency that becoming fragile.

As water system bonding agent main component and example when using polyurethane resin, as adhesive composite appropriate Son can enumerate the mixture of Polyester ionomer type polyurethane resin with the compound with glycidyl oxygroup.Herein Described Polyester ionomer type polyurethane resin refers to the polyurethane resin with polyester backbone, and has imported wherein a small amount of Ionic ingredient (hydrophilic component) substance.Ionomer type polyurethane resin is not in the case where using emulsifier directly in water Middle emulsification forms emulsion, therefore is suitable for being used as water-based bonding agent.Polyester ionomer type polyurethane resin is used to be bonded Polarizing coating and this item of protective film are recorded in such as Japanese Unexamined Patent Publication 2005-70139 bulletin, Japanese Unexamined Patent Publication No. 2005-70140 number Bulletin, Japanese Unexamined Patent Publication 2005-181817 bulletin.

On the other hand, using energy ray-curable bonding agent is activated, constitute it passes through active-energy The irradiation of ray and cured ingredient (hereinafter sometimes referred to simply as " curability composition ") can be epoxide, oxa- ring fourth Hydride compounds, (methyl) acrylic compounds etc..In the cation using epoxide, oxetane compound etc In the case where the compound of polymerism, cooperate cationic polymerization initiators.In addition, use (methyl) acrylic compounds it In the case where the free-radical polymerised compound of class, cooperate radical polymerization initiator.Wherein, preferably using epoxide as Direct Bonding on saturated carbon ring is particularly preferably had the cycloaliphatic epoxy of epoxy group by the bonding agent of one of curability composition Bonding agent as one of curability composition.In addition, being also effective to it and with oxetane compound.

The commercially available product of epoxide can be readily available, for example, having respectively for trade name by Japan " EPIKOTE " that Epoxy Resin Corporation is sold series, " EPICRON " series sold by Dainippon Ink Chemicals, " ADEKA RESIN " system that " EPOTOHTO " sold by Toto Kasei KK is serial, is sold by Asahi Denka Co., Ltd. Column, " Denacol " sold by Nagase ChemteX Corporation series are sold by Dow Chemical Company " Dow Epoxy " series, " TEPIC " that is sold by Nissan Chemical Ind Ltd etc..

Direct Bonding has the commercially available product of the cycloaliphatic epoxy of epoxy group that can also easily obtain on saturated carbon ring , for example, respectively for trade name, have " Celloxide " series sold by Daisel chemical industry Co., Ltd and " Cyclomer " series, by Dow Chemical Company " CYRACURE " series sold etc..

The commercially available product of oxetane compound can also be readily available, for example, having respectively for trade name by east " ETERNACOLL " that " the ARONE OXETANE " that Asia synthesis Co., Ltd. sells is serial, is sold by Ube Industries, Ltd Series etc..

The commercially available product of cationic polymerization initiators can also be readily available, such as respectively for trade name, be had by day " Cyracure " that " KAYARAD " that this chemical drug Co., Ltd. sells is serial, is sold by Union Carbide Corporation Series, the photoacid generator " CPI " sold by San-Apro Ltd series, by Midori Kagaku Co., light that Ltd is sold produces Sour agent " TAZ ", " BBI " and " DTS ", " the ADEKA OPTOMER " sold by Asahi Denka Co., Ltd. series, by Rhodia company " RHODORSIL " series sold etc..

Active energy ray-curable bonding agent can according to need containing photosensitizer.By using photosensitizer, reactivity It improves, mechanical strength, the adhesive strength of adhesive layer can be further increased.As photosensitizer, it can be cited for example that carbonylation Close object, organosulfur compound, persulfide, redox based compound, azo and two azo-compounds, anthracene based compound, halogen Compound, photo-reduction pigment etc..

In addition, can cooperate in the range of not destroying its cementability each for active energy ray-curable bonding agent Kind additive.As additive, it can be cited for example that ion capturing agent, antioxidant, chain-transferring agent, tackifier, thermoplastic resin Rouge, filler, flow modifier, plasticizer, defoaming agent etc..Further, in the range of not damaging its cementability, can also match Close the cured curability composition under the reaction mechanism different from cationic polymerization.

When carrying out the fitting of film using active energy ray-curable bonding agent, film is pasted by the inclusion of the layer of the bonding agent After conjunction, irradiation active energy beam solidifies adhesive layer.In the active energy ray-curable that a face of polarizing coating uses Bonding agent in the active energy ray-curable bonding agent that another face uses can be same composition, be also possible to different groups At preferably carrying out the irradiation for both making cured active energy beam simultaneously.

Cured active energy beam for active energy ray-curable bonding agent can be for example wavelength be 1~ The luminous ray etc. that ultraviolet light that the X-ray of 10nm, wavelength are 10~400nm, wavelength are 400~800nm.Wherein, it is utilizing Easy degree and the easy degree of preparation of active energy ray-curable bonding agent, stability and curing performance side It is preferable to use ultraviolet lights in face.For the light source of ultraviolet light, it can be used for example below wavelength 400nm to have to shine and divide Cloth, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black light lamp, microwave-excitation mercury Lamp, metal halide lamp etc..

Thickness using adhesive layer obtained by active energy ray-curable bonding agent is usually 1~50 μm or so, special Not preferably in the range of 1~10 μm.

Since polarization plates of the invention are used as fitting using (methyl) acrylic resin film of the invention or stretched film In the polarization plates of the protective film of polarizing coating, therefore, be also less likely to occur even in a high temperature environment deformation, optical characteristics it is bad Change, excellent heat resistance.

Polarization plates of the invention can suitably be used as the polarization plates for constituting liquid crystal display panel used in liquid crystal display device, It is particularly suitable as being configured at the polarization plates depending on recognizing side of liquid crystal cell.The view of liquid crystal cell is configured in polarization plates of the invention In the case where recognizing side, the polarization plates for being configured at the back side of liquid crystal cell can be polarization plates of the invention, be also possible to other Polarization plates.The liquid crystal cell for constituting liquid crystal display panel can be the various elements used in the field.

Fitting of the polarization plates to liquid crystal cell can be carried out by the adhesive phase formed in advance on the surface of polarization plates. The adhesive phase can be layered on a protective film possessed by polarization plates, for example, being fitted with this in a face of polarizing coating (methyl) acrylic resin film or stretched film, another face of invention are fitted in the polarization plates of other transparent resin films, can Adhesive phase is arranged in the outer surface of transparent resin film.If passing through adhesive phase using the polarization plates as depending on recognizing lateral deviation vibration plate Liquid crystal cell is fitted in, then becomes (methyl) acrylic resin film or stretched film is configured at the liquid crystal display panel depending on recognizing side.

Adhesive phase is generally utilized using (methyl) acrylate as main component, containing functional group (methyl) acrylic acid series list Body copolymerization made of (methyl) acrylic resin be adhesive ingredients (methyl) acrylic adhesive and formed.

Embodiment

Hereinafter, showing embodiment is further elaborated with the present invention, but the present invention is not limited by these examples.In example, The % and part for indicating content or usage amount are exactly weight basis unless otherwise specified.

In following Examples and Comparative Examples, made using resin described in following (A) (hereinafter referred to as " Resin A ") For (methyl) acrylic resin A, using resin described in following (B1) or (B2) (hereinafter, be referred to as " resin B 1 ", " resin B 2 ") it is used as (methyl) acrylic resin B.

Methyl methacrylate system resin " ALTUGLAS HT121 " (glass transition temperature of (A) ARKEMA corporation T_gA: 124 DEG C, weight average molecular weight M_wA: 78200, number-average molecular weight M_nA: 41200, molecular weight dispersion M_wA/M_nA: 1.9),

(B1) includes the methyl methacrylate system resin of 80% or more the Component units from methyl methacrylate (glass transition temperature T_gB: 110 DEG C, weight average molecular weight M_wB: 162000, number-average molecular weight M_nB: 84500, molecular weight dispersion M_wB/ M_nB: 1.9),

(B2) includes the methyl methacrylate system resin of 80% or more the Component units from methyl methacrylate (glass transition temperature T_gB: 107 DEG C, weight average molecular weight M_wB: 134000, number-average molecular weight M_nB: 67000, molecular weight dispersion M_wB/ M_nB: 2.0).

1 > of < embodiment

By granular Resin A and granular resin B 1 with the weight ratio of 75:25 puts into extruder and forms (methyl) Acrylic resin composition obtains the melting mixing object of liquid and carrying out melting mixing by being heated.While by the melting The hybrid resin of the liquid of mixing is continuously extruded into membranaceous from T mould, while being solidified using chill roll, thus makes thickness (methyl) acrylic resin film (non-stretched product) of 120 μm of long size.

In addition, the stretched film of 96 μm of thickness of production is (vertical to stretch by implementing vertical single ax stretch processing to above-mentioned non-stretched product Product).Draft temperature is set as+10 DEG C of glass transition temperature of non-stretched product (i.e. above-mentioned hybrid resin), and stretching ratio is set as 2.2 Times.

Further, by implementing after above-mentioned non-stretched product are implemented with vertical stretch processing, implementing horizontal stretch processing gradually Biaxial stretch-formed processing, the stretched film (vertically and horizontally stretching product) of 40 μm of thickness of production.Draft temperature is all provided in vertical stretching and horizontal stretching It is+10 DEG C of glass transition temperature of non-stretched product (that is, above-mentioned hybrid resin), indulges the stretching ratio difference of stretching and horizontal stretching It is set as 2.2 times, 2.0 times.

< embodiment 2~4,1~4 > of comparative example

As the resin combination of the production for (methyl) acrylic resin film (non-stretched product), in addition to using table 1 Other than the hybrid resin (melting mixing object) or single resin, (methyl) acrylic acid has been made similarly to Example 1 Resin film (non-stretched product).In addition, using the non-stretched product, vertical stretching product and/or in length and breadth have been made similarly to Example 1 Stretching product.It should be noted that the rubber particles that Resin A is matched in comparative example 2 are the elastomer particles of three-decker, In, innermost layer includes the poly- of the hard being polymerized using methyl methacrylate and a small amount of allyl methacrylate Object is closed, middle layer includes using butyl acrylate as main component, further uses styrene and a small amount of methacrylic acid allyl The soft elastomer that ester is polymerized, outermost layer include using methyl methacrylate and a small amount of ethyl acrylate into The polymer for the hard that row is polymerized uses the elasticity that the average grain diameter until the elastomer as middle layer is 240nm Body particle.

Following physical property are measured to hybrid resin used in each Examples and Comparative Examples (melting mixing object) or single resin, And following evaluation tests is carried out to non-stretched product obtained in each Examples and Comparative Examples, vertical stretching product, vertically and horizontally stretching product.Knot Fruit is shown in table 1.

(1) weight average molecular weight of hybrid resin or single resin, number-average molecular weight and molecular weight dispersion

Granular hybrid resin will be formed or granular single resin 40mg is dissolved in tetrahydrofuran 20mL and makes Standby measurement sample, measures dissolution time and intensity using GPC device.By these measured values, with bent using the standard of standard sample On the basis of line, weight average molecular weight M is found out_w, number-average molecular weight M_n, calculate molecular weight dispersion M_w/M_n。

The detailed content of GPC determination condition is as follows.

GPC device: " HLC-8320GPC " of Tosoh (strain) system,

Gel permeation chromatographic column: being " TSKgel-SuperHZ2500 " 1 and " TSKgel- for making Tosoh (strain) 2 columns being connected in series of SuperHRC ",

Column temperature: 40 DEG C,

Detector: RI detector,

Measurement sample injection rate: 20 μ L,

Mobile phase: tetrahydrofuran,

The flow velocity of mobile phase: 1.0mL/ minutes,

Standard sample: 7 kinds of monodisperse methyl methacrylates (are Showa electrician (strain) known to weight average molecular weight System).

(2) glass transition temperature of hybrid resin or single resin

Using DSC device [" DSC7020 " of Seiko Instruments Inc.], according to based on JIS K7121: 1987 differentia scanning calorimetry, under nitrogen flow 100ml/ minutes, by granular hybrid resin or granular list One resin is warming up to 150 DEG C with 20 DEG C/min of heating rate, keeps after five minutes, be cooled to 10 DEG C/min of cooling rate- It 50 DEG C, is kept for 1 minute.Next, being warming up to 210 DEG C from -50 DEG C with 10 DEG C/min of heating rate, intermediate point glass is found out Change transition temperature (Tmg), as glass transition temperature.The value is bigger, more shows heat resistance height.

(3) evaluation of the toughness of non-stretched product or stretching product

(3-1) Mandrel test

With mechanical squeeze out direction (MD) of film for length direction, by the test film of film cut-out length 120mm, width 10mm. For the test film, the resistance to bend(ing) testing machine (cylinder method mandrel method) of Co. Ltd. system is ground using TP skill, wound on cylindrical shape Axis around, make test film along the curved bent spindle test of its width direction, find out film do not generate breakage, notch, The minimum diameter of the axis of cracking, fracture.The value of the minimum diameter is smaller, then the toughness of film is the better, operational and processability is got over It is excellent.Mandrel test carries out non-stretched product and vertical stretching product.

(3-2) Sha Erpi (シ ャ Le ピ ー) impact test

According to JIS K 7111:2006 " plastics-Sha Erpi impact characteristics ask Fa-the 1: non-meter dressization impact test " Specified in be measured for the charpy impact test of the impact absorbing energy that measures plastics.Specifically, firstly, with film Mechanical squeeze out direction (MD) be length direction, by the test film of film cut-out length 82mm, width 10mm.Above-mentioned JIS standard pair It is provided using the case where test film with notch (ノ ッ チ) and using the case where not test film of notch, in this hair The bright middle test film using not notch.Then, it will be tested according to the motionless mode of test film under the impact when being punched with hammer Supporting table is fixed at the longitudinal direction both ends of piece, makees made charpy impact tester using Co., Ltd.'s peace field essence mechanism (hammer weighing 1.0J), will hammer the side parallel with width direction in the length direction central portion of test film according to its blade tip length direction into shape Formula is beaten, energy needed for measuring the fracture of film (impact absorbing energy, mJ).Impact absorbing energy is bigger, then film is not more It is easy to produce breakage, notch, cracking, fracture, toughness is good, operability and excellent in workability.Sha Erpi impact absorbing energy Measurement carries out non-stretched product.

(3-3) is made film breaks when vertical stretching product by non-stretched product

It measures under above-mentioned stretching condition by the vertical stretching product of non-stretched product production certain length (about 50m) of long size The breaks of the film of Shi Fasheng.Breaks are fewer, then the toughness of film is the better, processability is more excellent.

(4) evaluation of the heat resistance of non-stretched product or stretching product

The measurement of (4-1) heat shrink rate

With mechanical squeeze out direction (MD) of film for length direction, by film cut-out length 120mm, the width (direction TD: orthogonal with MD Direction) test film of 120mm encloses mark in the place (at 2) of distance center portion 50mm respectively for the direction MD and the direction TD Note.The heat run for standing 10 minutes in 100 DEG C of baking oven is carried out to the test film.It is measured and is heated using digital vernier slide calliper rule The size changing amount (length between label) on the direction MD and the direction TD of front and back is tested, respectively for the direction MD and the direction TD, According to following formula:

Heat shrink rate (%)=100 × (length after length-heating before heating)/(length before heating)

Find out heat shrink rate (%).Heat shrink rate is smaller, then heat resistance is more excellent.The measurement of heat shrink rate is not to Stretching product and vertically and horizontally stretching product carry out.

The measurement of (4-2) drawing by high temperature elasticity modulus

Using cupping machine (" the Autograph AG-1 " of Shimadzu Scisakusho Ltd), in 80 DEG C of ring of temperature Tension test is carried out with 1mm/ minutes conditions of tensile speed under border, measures the tensile modulus of elasticity (MPa) of film.The tensile elasticity Modulus is higher, then heat resistance is more excellent.The measurement of drawing by high temperature elasticity modulus carries out vertically and horizontally stretching product.

Table 1

Claims (7)

1. a kind of (methyl) acrylic resin composition, it includes:

(methyl) acrylic resin A and

(the first that and weight average molecular weight lower than the glass transition temperature of (methyl) the acrylic resin A is 100000 or more Base) acrylic resin B,

The content ratio of (methyl) acrylic resin A and (methyl) acrylic resin B is 90/10~10/ with weight ratio meter 90。

2. (methyl) acrylic resin composition as described in claim 1, wherein

The vitrifying of the glass transition temperature of (methyl) the acrylic resin A and (methyl) the acrylic resin B The difference of transition temperature is 20 DEG C or less.

3. (methyl) acrylic resin composition as claimed in claim 1 or 2, is (methyl) acrylic resin The melting mixing object of A and (methyl) the acrylic resin B.

4. a kind of (methyl) acrylic resin film, it includes (methyl) acrylic resin compositions described in claim 1.

5. a kind of stretched film is made of stretching (methyl) acrylic resin film as claimed in claim 4.

6. a kind of polarization plates, it includes:

Polarizing coating and

In (methyl) acrylic resin film or claim as claimed in claim 4 that at least one side of the polarizing coating is laminated Stretched film described in 5.

7. polarization plates as claimed in claim 6, wherein

It is laminated with (methyl) acrylic resin film or the stretched film on one side in the polarizing coating, is laminated in another side There are other transparent resin films.