TWI680054B - Optical surface protective film with separator - Google Patents

Abstract

The invention relates to an optical surface protection film with a separator, which has a polyester film on one side of the adhesive layer and a separator on the side of the adhesive layer opposite to the polyester film. The Si-Kα line strength of the surface protective film for optical parts of the adhesive layer after the separator is peeled off under fluorescent X-rays is 2.5 kcps or less. The peeling force of the separator on the optical surface protective film is When the stretching speed is 0.3 m / min, it is 0.5 N / 50 mm or less. The optical surface protection film with a separator can prevent the peeling of other layers such as an interlayer filler (layer) provided on the surface of the adhesive body after the surface protective film is peeled from the adhesive body.

Description

Optical surface protective film with separator Field of invention

The present invention relates to an optical surface protection film with a separator.

The optical surface protection film with a separator of the present invention may be used as an optical surface protection film for the purpose of protecting the surface of an optical component. The optical component may be glass, a polarizer, or a wavelength used for a liquid crystal display or the like. Sheet, phase retarder, optical compensation film, reflective sheet, brightness enhancement film, and transparent conductive film.

Background of the invention

In the past, in order to prevent the surface of an optical component or an electronic component from being damaged during processing, assembly, inspection, and transportation, a surface protection film was generally attached to the exposed surface of the component. The surface protection film is composed of a base film and an adhesive layer. According to requirements, a separator (release film, or release film) is attached to the surface of the adhesive for the purpose of protecting the adhesive layer before being applied (used). Cover paper) (Patent Document 1). The optical surface protection film with a separator is attached to an optical component as an adhesive body after the separator is peeled off.

After the attached surface protection film is peeled from the optical component when it is not needed, it may be provided on the surface of the optical component after peeling. Layers of other functions (other layers), etc. (Patent Document 2).

Advance technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2012-224811

Patent Document 2: Japanese Patent Laid-Open No. 2014-208756

Summary of invention

However, due to the state of the surface of the optical component (adhesive body) after peeling the surface protection film, the wettability or adhesion to other layers is deteriorated, which causes the other layers to peel off from the optical component, and the product is defective. . In particular, when an optical surface protective film with a separator is used, it is provided on another layer (such as an interlayer filler (layer)) of an adherend (for example, a glass surface constituting an optical part) after the optical surface protective film is peeled off. There is a problem of easy peeling. Therefore, it is necessary to develop an optical surface protective film with a separator, which can ensure that it is difficult to peel off when other layers such as interlayer fillers (layers) are provided on the adherend such as the glass surface after the surface protective film has been peeled. .

The object of the present invention is to provide an optical surface protection film with a separator, which can protect the optical parts of the adherend from being damaged by dirt and scratches, and can be prevented from being provided on the surface of the adherend after the surface protective film is peeled from the adherend Other layers such as interlayer fillers (layers) tend to peel off easily.

The present inventors have conducted intensive studies in view of the foregoing circumstances, and have developed In the optical surface protective film with a separator, when the adhesive layer after the separator is peeled is attached to an adherend such as glass and then peeled off, the components of the adhesive layer will remain on the adherend, contaminating the adhesive. The surface of the body affects the ease of peeling of other layers, such as interlayer fillers (layers), which are then provided on the adherend. Therefore, it was found that it is possible to provide an optical surface protective film with a separator, and by using the optical surface protective film with a separator having a specific parameter, it is possible to peel off the adherend after the optical surface protective film is peeled off compared to the past. The effect of surface contamination is reduced, and peeling of other layers such as interlayer fillers (layers) can be prevented.

That is, the present invention relates to an optical surface protection film with a separator having a polyester film on one side of the adhesive layer and a separator on the side opposite to the polyester film of the adhesive layer. In the optical surface protection film of an optical element, the Si-Kα line strength of the surface of the adhesive layer under fluorescent X-rays after peeling the separator is 2.5 kcps or less, and the peeling force of the separator to the optical surface protection film At a stretching speed of 0.3 m / min, it is 0.5 N / 50 mm or less.

The optical surface protection film with a separator of the present invention is preferably such that the separator has a release layer and a substrate, and the release layer is made of a mold containing a long-chain alkyl-based material and / or an aliphatic carboxylic acid ester. Agent composition is formed.

The optical surface protection film with a separator of the present invention is preferably such that the aforementioned adhesive layer is an adhesive composition containing a (meth) acrylic polymer (A) and an aliphatic polyisocyanate crosslinking agent (B) Formed; the (meth) acrylic polymer (A) contains at least one (Meth) acrylic monomers and hydroxyl-containing (meth) acrylic monomers are used as monomer components, and the glass transition temperature is -50 ° C or lower; 100 parts by weight of a (meth) acrylic monomer, and 2 to 20 parts by weight of the hydroxyl-containing (meth) acrylic monomer.

The optical surface protection film with a separator of the present invention preferably contains 1 to 30 weights of the aforementioned aliphatic polyisocyanate-based crosslinking agent (B) based on 100 parts by weight of the (meth) acrylic polymer (A). Serving.

In the optical surface protective film with a separator according to the present invention, the aforementioned adhesive composition preferably further contains a catalyst (C) having iron or tin as an active center.

In the optical surface protective film with a separator of the present invention, it is preferable that the catalyst (C) containing iron or tin as the active center is 0.002 to 100 parts by weight of the (meth) acrylic polymer (A). 0.5 parts by weight.

The optical surface protective film with a separator of the present invention has excellent peelability from the optical surface protective film and the separator, and the optical surface protective film after the separator is peeled off from the adherend is excellent. In the case of optical surface protection films, the effect of contamination on the surface of the adhesive caused by the adhesive layer is small, so that other layers such as interlayer fillers (layers) that are disposed on the adhesive can be prevented from peeling off the adhesive, which is very useful.

1‧‧‧ divider

2‧‧‧ Optical surface protection film

3‧‧‧ Optical Surface Protective Film with Separator

11‧‧‧ Substrate

12‧‧‧ release layer

21‧‧‧Adhesive layer

22‧‧‧Polyester film

FIG. 1 is a schematic cross-sectional view showing a configuration example of an optical surface protective film with a separator according to the present invention.

Forms used to implement the invention

Hereinafter, embodiments of the present invention will be described in detail.

<Overall Structure of Optical Surface Protection Film with Separator>

The optical surface protection film of the present invention is an optical component such as glass used in glass, polarizer, wavelength plate, phase retarder, optical compensation film, reflection sheet, brightness enhancement film, and transparent conductive film used in liquid crystal displays and the like. Parts) Optical surface protection films used to protect the surface of optical parts during processing or handling. Generally speaking, there are types such as optical adhesive sheets, optical adhesive tapes, optical adhesive labels, and optical adhesive films. . The adhesive layer of the aforementioned optical surface protection film is typically formed continuously, but it is not limited to this type, and it may be an adhesive layer with regularity such as dots, stripes, or formed in a random pattern. The optical surface protection film may have a roll shape or a leaf shape.

FIG. 1 schematically shows a typical configuration example of the optical surface protective film with a separator according to the present invention. The optical surface protection film 3 with a separator is formed by laminating the separator 1 and the optical surface protection film 2. The separator 1 includes a base material 11 and a release layer 12; an optical surface protection film 2 includes a polyester film 22 and an adhesive layer 21 provided on one side thereof, and the release layer 12 and the adhesive layer 21 are pasted Layered together. After the separator 1 is peeled off, the surface protective film 3 for an optical member with a separator is adhered to the optical part of the adherend (protected object, for example, glass, polarizer, wavelength plate, Optical components such as phase retarders, optical compensation films, reflective sheets, brightness enhancement films, and transparent conductive films Surface), and is peeled from the optical component when it is not needed. In addition, the optical surface protection film 3 with a separator can be exemplified by those having an adhesive layer 2 on both sides of the polyester film 22, or an antistatic surface on the opposite side of the surface of the polyester film 22 having the adhesive layer 2. Layers.

<Optical Surface Protective Film>

The optical surface protection film of the present invention includes a polyester film and an adhesive layer.

<Polyester film>

Examples of the polyester film of the present invention include ester bonds such as polyethylene terephthalate (PET), polyethylene terephthalate (PEN), and polybutylene terephthalate. The polymer material (polyester resin) of the basic main skeleton is the main resin component. The aforementioned polyester film has excellent optical characteristics and stability of specifications, but has a property of being easily charged in its original state.

To the resin material constituting the aforementioned polyester film, various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (pigment, dye, etc.) may be added as necessary. The first surface of the aforementioned polyester film may be subjected to a known or customary surface treatment such as a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, and a primer application. Such a surface treatment can be used to improve the adhesion between the polyester film and the adhesive layer (anchorability of the adhesive layer). For example, a surface treatment in which a polar group such as a hydroxyl group (-OH group) is introduced on the surface of the polyester film is preferably used. The second surface of the polyester film may be subjected to the same surface treatment as described above, or an adhesive layer or an antistatic layer may be provided.

In the optical surface protection film of the present invention, The antistatic layer is provided on the opposite side of the polyester film from the surface to which the adhesive layer is attached, and can provide an antistatic function. Further, a polyester film which has been subjected to an antistatic treatment in advance may be used. By using the aforementioned polyester film, it is preferable to suppress the electrification when peeling the separator and peeling the adhesive layer from the optical part of the adherend, so it is preferable. The method for imparting antistatic function is not particularly limited, and conventional methods can be used, such as coating an antistatic resin composed of an antistatic agent and a resin component, or the conductivity of a conductive polymer or a conductive substance. The method of resin, or the method of vapor-depositing or electroplating a conductive substance, the method of mixing an antistatic agent, etc. are mentioned.

The thickness of the polyester film is usually 5 to 200 μm, and preferably about 10 to 100 μm. When the thickness of the polyester film is within the aforementioned range, it is preferable because it is excellent in attaching workability to an optical component as an adherend and workability of peeling from the optical component.

<Adhesive layer>

The adhesive layer of the present invention is formed of an adhesive composition that does not substantially contain a polysiloxane material. The “substantially free of polysiloxane material” means that the intensity of the Si-Kα line of the surface of the adhesive layer under fluorescent X-rays is 2.5 kcps or less. The adhesive composition is not particularly limited as long as it has an adhesive substance. For example, an acrylic adhesive composition, a urethane adhesive composition, a synthetic rubber adhesive composition, and natural rubber can be used. As the adhesive composition, etc., an acrylic adhesive composition is preferably used.

<(Meth) acrylic polymer (A)>

The acrylic adhesive composition contains (meth) acrylic polymerization 物 (A). The (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer.

<(Meth) acrylic monomer containing 2 to 14 carbon atoms>

The aforementioned (meth) acrylic polymer (A) is not particularly limited as long as it is a (meth) acrylic polymer having adhesive properties. As the main component of the monomer component, it is preferable to use a carbon containing 2 to 14 alkyl groups. (Meth) acrylic monomer. As the (meth) acrylic monomer having a carbon number of 2 to 14 alkyl groups, one kind or two or more kinds can be used as a main component. In addition, the main component means the highest allocation ratio.

Specific examples of the (meth) acrylic monomer containing 2 to 14 alkyl groups include ethyl (meth) acrylate, n-butyl (meth) acrylate, and secondary (meth) acrylic acid. Butyl ester, tertiary butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate , Isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) N-dodecyl acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.

Among them, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, and (meth) are more suitable. N-nonyl acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, iso-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-thirteen (meth) acrylate (Meth) acrylic monomers containing 6 to 14 alkyl groups, such as esters and n-tetradecyl (meth) acrylate. By using the aforementioned (meth) acrylic monomer containing 6 to 14 alkyl groups, it is possible to easily control and reduce the The adhesive force of the adherend becomes an adhesive layer with excellent re-peelability.

In the (meth) acrylic polymer (A), the (meth) acrylic polymer (A) contains the (2 to 14 alkyl groups) ( The meth) acrylic monomer is preferably 50 to 99% by weight, more preferably 60 to 98% by weight, more preferably 70 to 97% by weight, and most preferably 80 to 96% by weight. If it is within this range, the adhesive composition will have moderate wettability and the adhesive force of the adhesive layer will also be excellent, so it is preferable.

<Hydroxy-containing (meth) acrylic monomer>

The (meth) acrylic polymer (A) preferably contains a hydroxyl group-containing (meth) acrylic monomer as a monomer component. By containing the aforementioned (meth) acrylic monomer containing a hydroxyl group, the hydroxyl group can easily control the crosslinking, improve the wettability of the flow, and easily control the balance of the cohesive force and the shear force of the aforementioned adhesive layer. In addition, when an antistatic agent is added to the aforementioned adhesive layer, unlike a carboxyl group or a sulfonic acid group, which generally functions as a cross-linking site, a hydroxyl group can have a moderate interaction with an ionic compound of the antistatic agent. The electrostatic viewpoint is also suitable for use.

Examples of the hydroxyl-containing (meth) acrylic monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) Acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate , (4-hydroxymethylcyclohexyl) methacrylate, N-hydroxymethyl (meth) acrylamide, and the like. The aforementioned (meth) acrylic monomer containing a hydroxyl group may be used alone or as a mixture of two or more kinds.

In the (meth) acrylic polymer (A), the carbon-containing polymer is used. When the (meth) acrylic monomer having 2 to 14 alkyl groups and the (meth) acrylic monomer having a hydroxyl group are used, the (meth) acrylic monomer having 2 to 14 alkyl groups 100 parts by weight, the aforementioned hydroxyl-containing (meth) acrylic monomer is preferably 2 to 20 parts by weight, more preferably 3 to 15 parts by weight, and even more preferably 4 to 12 parts by weight. If it is within this range, it is easier to control the balance between the wettability of the adhesive composition and the cohesive force and shear force of the adhesive layer, so it is preferable.

<Carboxy-containing (meth) acrylic monomer>

The (meth) acrylic polymer (A) preferably contains a carboxyl group-containing (meth) acrylic monomer as a monomer component. By containing the carboxyl group-containing (meth) acrylic monomer, the carboxyl group can improve the shear force, and can prevent an increase in the adhesive force with the passage of time. Adhesive layer. In particular, by improving the shear force of the adhesive layer, the adhesive layer can suppress curling along the adhesive body when it is attached to the adhesive body, and can prevent slippage between the adhesive layer and the adhesive body (interface). Shift or misplace.

Examples of the carboxyl group-containing (meth) acrylic monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acrylic acid. Ethoxyethyl hexahydrophthalate, 2- (meth) acrylic ethoxypropyl hexahydrophthalate, 2- (meth) acrylic ethoxyethyl phthalate, 2- (methyl ) Acrylic ethoxyethyl succinate, 2- (meth) acrylic ethoxyethyl maleate, carboxy polycaprolactone mono (meth) acrylate, 2- (meth) acrylic ethoxy Ethyl tetrahydrophthalate and the like. The carboxyl group-containing (meth) acrylic monomer may be used alone or in combination of two or more.

In the (meth) acrylic polymer (A), the carbon-containing polymer is used. When the (meth) acrylic monomer having 2 to 14 alkyl groups and the (meth) acrylic monomer having a carboxyl group are used, the (meth) acrylic monomer having 2 to 14 alkyl groups 100 parts by weight, the aforementioned carboxyl group-containing (meth) acrylic monomer is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.8 part by weight, more preferably 0.01 to 0.5 part by weight, and most preferably 0.02 to 0.2 part by weight Serving. If it is within this range, it can suppress the increase of the adhesive force caused by the adhesive layer over time, and has excellent re-peelability, preventability of increase in adhesive force, and workability, and also the shear force and the cohesive force of the adhesive layer It is also excellent, so it is better.

<Other polymerizable monomers>

In the (meth) acrylic polymer (A), other polymerizable monomers may be used as the monomer component, and there is no particular limitation as long as it does not impair the characteristics of the present invention. In particular, the aforementioned other polymerizable monomers are used to adjust the glass transition temperature and peelability for the reason that the adhesive performance balance can be easily achieved, so that the Tg of the (meth) acrylic polymer (A) becomes -50. Below -100 ° C.

As the aforementioned other polymerizable monomers, cyano-containing monomers, vinyl ester monomers, aromatic vinyl monomers and the like can be suitably used to improve the cohesive force. Heat-resistant components, and fluorene-containing monomers, fluorenimine-containing monomers, amine-containing monomers, epoxy-containing monomers, N-acrylic fluorenyl morpholine, vinyl ether monomers, etc. A component that enhances adhesion (adhesion) and a functional group that functions as a crosslinking point. These polymerizable monomers may be used alone or in combination of two or more.

Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl dodecanoate.

Examples of the aromatic vinyl monomer include styrene, chlorinated styrene, chloromethylated styrene, α-methylstyrene, and other substituted styrenes.

Examples of the amidino group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N'-methylenebisacrylamide, N, N -Dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamine, diacetoneacrylamide and the like.

Examples of the fluorenimine-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconicimine, and the like.

Examples of the amine-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (Meth) acrylate and the like.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, allyl glycidyl ether, and the like.

Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.

Relative to the total amount of the monomer components constituting the (meth) acrylic polymer (A), the other polymerizable monomer is preferably 0.01 to 1% by weight, and more preferably It is 0.05 to 0.5% by weight. Because the aforementioned other polymerizable monomers are used within this range, for example, when an ionic compound of an antistatic agent is used, it has a good interaction with the compound, and can adjust the good re-peelability appropriately.

The weight average molecular weight (Mw) of the aforementioned (meth) acrylic polymer (A) is 100,000 to 5 million, preferably 200,000 to 4 million, and more preferably 300,000 to 3 million. If the weight-average molecular weight is less than 100,000, the cohesive force of the adhesive composition becomes small, and there is a tendency that the paste remains. On the other hand, if the weight average molecular weight (Mw) exceeds 5 million, the fluidity of the polymer is reduced, and the wettability of the adherend (such as a polarizer of an optical part) is insufficient. The tendency to cause swelling. The weight-average molecular weight (Mw) is measured by GPC (gel permeation chromatography).

The glass transition temperature (Tg) of the (meth) acrylic polymer (A) is preferably -50 ° C or lower, more preferably -55 ° C or lower, and even more preferably -60 ° C or lower. The glass transition temperature (Tg) of the (meth) acrylic polymer is preferably -100 ° C or higher. If the glass transition temperature is higher than -50 ° C, the polymer will not flow easily. For example, the wettability of the adherend (such as polarizers of optical parts) will be insufficient, which will cause expansion between the adherend and the adhesive layer. The cause of the tendency. In particular, by setting the glass transition temperature to -61 ° C or lower, it is easy to obtain an adhesive composition having excellent wettability and light peelability to an adherend. The glass transition temperature of the (meth) acrylic polymer (A) can be adjusted within the aforementioned range by appropriately changing the monomer component or composition ratio used.

The polymerization method of the (meth) acrylic polymer (A) is not particularly limited, and solution polymerization, emulsion polymerization, block polymerization, and suspension can be used. Polymerization is carried out by a known method such as polymerization. However, particularly from the viewpoint of workability and characteristics such as low contamination with respect to an adherend, the preferred aspect is solution polymerization. The obtained polymer may be any of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

The adhesive composition preferably contains a crosslinking agent. As the aforementioned crosslinking agent, an isocyanate compound, an epoxy compound, a melamine-based resin, an aziridine derivative, and a metal chelate compound can be used. In particular, the use of an isocyanate compound is preferred. These compounds may be used alone or in combination of two or more.

<Aliphatic polyisocyanate-based crosslinking agent (B)>

Among the isocyanate compounds, the adhesive composition preferably contains an aliphatic polyisocyanate-based crosslinking agent (B). For example, when the adhesive composition contains the (meth) acrylic polymer (A), the constitutional unit, composition ratio, and aliphatic polyisocyanate of the (meth) acrylic polymer (A) are appropriately adjusted. The cross-linking agent (B) is selected and added in a ratio to cross-link it to obtain an adhesive layer having more excellent heat resistance.

Examples of the aliphatic polyisocyanate-based crosslinking agent (B) include aliphatic polyisocyanates such as trimethylene diisocyanate, butene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate. ; Aliphatic isocyanates such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate (IPDI); the aforementioned isocyanate compounds are bonded with urethane, biuret, and trimeric isocyanate Modified polyisocyanates, including uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, oxadiazine trione bonds, etc. Ester Modifiers. For example, as commercially available products, the trade names TAKENATE 300S, TAKENATE 500, TAKENATE D165N, TAKENATE D178N (the above are manufactured by Takeda Pharmaceutical Industry Co., Ltd.); Sumidur T80, Sumidur L, Desmodur N3400 (the above is Sumika Bayer ammonia) Ester Co., Ltd.); Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (the above are manufactured by Japan Polyurethane Industry Co., Ltd.) and so on. The aliphatic polyisocyanate-based crosslinking agent (B) may be used singly or in combination of two or more kinds. A bifunctional isocyanate compound and a trifunctional or more isocyanate compound may be used in combination. By using a cross-linking agent in combination, it is possible to achieve the best of both adhesion and anti-reversion (adhesion to curved surfaces), and a surface protection film with more excellent adhesion reliability can be obtained.

The content of the aliphatic polyisocyanate-based crosslinking agent (B) is, for example, preferably from 1 to 30 parts by weight based on 100 parts by weight of the (meth) acrylic polymer (A), and more preferably Contains 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, and most preferably 3 to 6 parts by weight. When the content is less than 1 part by mass, the cross-linking formation of the cross-linking agent becomes insufficient, the cohesive force of the obtained adhesive layer becomes small, and sufficient heat resistance may not be obtained, and it may become a paste residue. The tendency to cause. On the other hand, if the content exceeds 30 parts by weight, the cohesive force of the polymer will increase, and the fluidity will decrease. For adherends (such as glass used in liquid crystal displays, polarizers, wavelength plates, phase retarders, optical compensation films, Optical components such as reflective sheets, brightness enhancement films, and transparent conductive films) have insufficient wettability and tend to cause swelling between the adherend and the adhesive layer. In addition, if the amount of cross-linking is too large, there is a tendency to decrease the peeling charging characteristics.

<Catalyst (C)>

The adhesive composition may further contain a catalyst (C) in order to make the crosslinking reaction proceed more efficiently. Examples of the catalyst (C) include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; iron (acetylacetone) iron, and iron (hexane-2,4-dione) , Ginseng (heptane-2,4-dione) iron, ginseng (heptane-3,5-dione) iron, ginseng (5-methylhexane-2,4-dione) iron, ginseng (octyl Alkane-2,4-dione) iron, ginseng (6-methylheptane-2,4-dione) iron, ginseng (2,6-dimethylheptane-3,5-dione) iron, Ginseng (nonane-2,4-dione) iron, Ginseng (nonane-4,6-dione) iron, Ginseng (2,2,6,6-tetramethylheptane-3,5-dione ) Iron, ginseng (tridecane-6,8-dione) iron, ginseng (1-phenylbutane-1,3-dione) iron, ginseng (hexafluoroacetone acetone) iron, ginseng (acetamidine Ethyl acetate) iron, ginseng (acetic acid-n-propyl) iron, ginseng (acetic acid isopropyl) iron, ginseng (ethyl acetate-n-butyl) iron, ginseng (acetic acid-n-butyl) Base) iron, ginseng (ethyl acetate-tertiary butyl) iron, ginseng (propyl ethyl acetate) iron, ginsyl (propyl ethyl acetate) iron, ginsyl (propyl acetate-n-propyl) iron , Ginseng (propyl isopropyl acetate) iron, ginseng (propyl acetic acid-n-butyl) iron, ginseng (propyl acetic acid-secondary butyl) iron, ginseng (propyl acetic acid-tertiary butyl) iron, Ginseng (Benzyl Acetate) Iron, iron such as ginseng (dimethyl malonate), ginseng (diethyl malonate), trimethoxy iron, triethoxy iron, triisopropoxy iron, iron (III) chloride, etc. Catalyst. The catalyst (C) may be used singly or in combination of two or more kinds.

In addition, as the iron-based catalyst, an iron chelate is suitably used, and can be expressed, for example, by the general formula Fe (X) (Y) (Z). The iron chelate can be expressed as Fe (X) ₃ , Fe (X) ₂ (Y), Fe (X) (Y) ₂ , Fe (X) through the arrangement and combination of (X) (Y) (Z). (Y) One of (Z). Among the iron chelates Fe (X) (Y) (Z), (X) (Y) (Z) is a ligand relative to Fe, for example, when X, Y or Z is β-diketone, it is β -Diketones include acetoacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, 5-methyl-hexane-2 , 4-dione, octane-2,4-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-3,5-dione, nonane- 2,4-dione, nonane-4,6-dione, 2,2,6,6-tetramethylheptane-3,5-dione, tridecane-6,8-dione, 1 -Phenyl-butane-1,3-dione, hexafluoroacetone acetone, ascorbic acid and the like.

When X, Y or Z is a β-ketoester, examples of the β-ketoester include methyl ethyl acetate, ethyl ethyl acetate, n-propyl ethyl acetate, isopropyl ethyl acetate, and ethyl ethyl acetate N-butyl acetate, secondary butyl acetate, tertiary butyl acetate, methyl propyl acetate, ethyl propyl acetate, n-propyl propyl acetate, isopropyl propyl acetate, propyl acetic acid N-butyl ester, secondary butyl propionate, tertiary butyl propionate, benzyl acetoacetate, dimethyl malonate, diethyl malonate and the like.

In addition, an iron-based catalyst other than the iron chelate may be used, and for example, a compound of iron and an alkoxy group, a halogen atom, or a fluorenyl group may be used. For iron and alkoxy compounds, examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, tertiary Butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyl, phenoxy, cyclohexyloxy, benzyloxy, 1-benzylnaphthyloxy and the like.

For a compound of iron and a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

For the compound of iron and fluorenyloxy, the fluorenyloxy includes 2-ethylhexanoic acid, octanoic acid, naphthenic acid, and resin acids (pinstroic acid, neospinnic acid, d-pimaric acid, iso- d-Pearic acid, Lo Hansonic acid, Gluconic acid Aliphatic organic acids or benzoic acid based on adipic acid, citric acid, aspartic acid, α-ketoglutarate, malic acid, succinic acid, glycine, histamine and other amino acids , Aromatic acids such as cinnamic acid, p-oxycinnamic acid, etc.).

Among the aforementioned iron catalysts, from the viewpoints of reactivity and hardenability, an iron chelate having β-diketone as a ligand is preferred, and ginseng (acetamidine) iron is particularly preferably used.

The content (use amount) of the catalyst (C) is preferably 0.002 to 0.5 parts by mass, more preferably 0.005 to 0.3 parts by mass, and more preferably 100 parts by mass of the (meth) acrylic polymer (A). 0.01 to 0.1 parts by mass. If it is within this range, the speed of the cross-linking reaction when the adhesive layer is formed is fast, and the life of the adhesive composition also becomes long, so it is a preferable aspect.

In addition, the aforementioned adhesive composition may further contain a compound that causes keto-enol interdenaturation as a crosslinking delaying agent. For example, an adhesive composition containing an aliphatic polyisocyanate-based cross-linking agent (B) or an adhesive composition containing an aliphatic polyisocyanate-based cross-linking agent (B) can be used. Enol tautomeric compounds. Thus, the addition of the aliphatic polyisocyanate-based crosslinking agent (B) can suppress excessive viscosity increase and gelation of the adhesive composition, and can achieve the effect of extending the life of the adhesive composition. This technique is suitable for use when, for example, the aforementioned adhesive composition is in an organic solvent solution or a solventless form.

As the aforementioned compound which produces keto-enol interdenaturation, various β-dicarbonyl compounds can be used. Specific examples include acetoacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methyl Β-diketones such as methyl heptane-2,4-dione, 2,6-dimethylheptane-3,5-dione; methyl ethyl acetate, ethyl ethyl acetate, ethyl ethyl acetate Acetyl acetates such as propyl ester, tert-butyl acetoacetate, etc .; Propyl acetates such as ethyl propyl acetate, ethyl propyl acetate, isopropyl propyl acetate, tert-butyl propyl acetate; Isobutyl acetic acid ethyl acetate, isobutyl acetic acid ethyl acetate, isobutyl acetic acid isopropyl acetate, tert-butyl isobutyl acetic acid tertiary butyl acetate and the like; methyl malonate, ethyl malonate Malonates; etc. Among them, suitable compounds include acetoacetone and acetoacetate. Compounds that cause keto-enol interdenaturation can be used alone or in combination of two or more.

The content of the compound capable of generating keto-enol tautomerization with respect to 100 parts by mass of the (meth) acrylic polymer (A) may be, for example, 0.1 to 20 parts by weight, and usually 0.5 to 15 parts by weight (for example, 1 ~ 10 parts by weight) is appropriate. If the amount of the aforementioned compound is too small, the use effect may not be sufficiently exerted. On the other hand, if the aforementioned compound is used more than necessary, it may remain in the adhesive layer and the cohesive force may be reduced.

In addition, the aforementioned adhesive composition may contain other well-known additives, for example, powders such as colorants, pigments, surfactants, plasticizers, antistatic agents, adhesion-imparting agents, and low molecular weights may be appropriately added according to the use. Polymers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, foils, etc.

<Production of Optical Surface Protective Film>

The optical surface protection film has an adhesive layer formed of the adhesive composition on one side of the polyester film. In this case, it is generally adhesive The crosslinking of the adhesive composition is performed after the composition is applied, but an adhesive layer composed of the crosslinked adhesive composition may be transferred to a substrate or the like.

The method for forming an adhesive layer on a polyester film is not particularly limited. For example, a solution of the aforementioned adhesive composition is applied to a film, and a polymerization solvent and the like are dried and removed to form an adhesive layer on the film. Thereafter, the adjustment of the components of the adhesive layer or the adjustment of the cross-linking reaction may be performed for the purpose of curing. In addition, when the adhesive composition is coated on a polyester film to prepare an adhesive layer, one or more solvents other than a polymerization solvent may be newly added to the adhesive composition, so that it can be uniformly applied to the adhesive composition. On the film.

As a method for forming the adhesive layer, a known method for producing an adhesive layer can be used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brush coating, spray cloth, pneumatic blade coating method, squeeze coating method of a slit coater, and the like can be mentioned.

The thickness of the aforementioned adhesive layer is preferably from 3 to 100 μm, and is preferably made from about 5 to 50 μm. If the thickness of the adhesive layer is within this range, it is easy to obtain an appropriate balance between re-peelability and adhesion (adhesiveness), so it is preferable.

<Divider>

In the optical surface protection film of the present invention, a separator is attached to the surface of the adhesive layer for the purpose of protecting the aforementioned adhesive layer. The separator includes a substrate and a release layer.

<Substrate>

As the aforementioned substrates, such as paper and plastic films, plastic films are more suitable for use in terms of surface smoothness. As the film, as long as it can There is no particular limitation on the protection of the adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride copolymer film. , Polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the aforementioned substrate is usually 5 to 200 μm, and preferably about 10 to 100 μm. If it is within this range, it is excellent in the workability of attaching to the adhesive layer and the workability of peeling from the adhesive layer.

The surface of the substrate may be subjected to various surface treatments such as corona discharge treatment or various surface treatments such as embossing, if necessary. Various additives such as fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, colorants (pigments, dyes, etc.) can also be added as required. .

<Release layer>

The release layer has adhesiveness to the substrate and release property to the adhesive layer, and is formed of a release agent composition that does not substantially contain a polysiloxane material. The aforementioned "substantially polysilicone-free material" refers to the Si-Kα line strength (a) of the surface of the release layer of the separator under fluorescent X-rays and the surface of the substrate without the release layer of the separator (Untreated surface) The difference [(b)-(a)] of the Si-Kα line intensity (b) under fluorescent X-rays is 0.3 kcps or less.

The mold release agent composition preferably contains a long-chain alkyl-based material and / or an aliphatic carboxylic acid ester. Even if only a small amount of these compounds are added to the release agent composition, peelability is remarkably obtained, and the appearance of the coating layer formed from the release layer composition described above is not spotted or whitened, so it is preferable. The These compounds may be used alone or in combination of two or more.

<Long-chain alkyl-based material>

The long-chain alkyl-based material refers to a compound having a linear or branched alkyl group having a carbon number of 6 or more, preferably 8 or more, and more preferably 12 or more. Examples of the alkyl group include octyl, decyl, dodecyl, octadecyl, and behenyl. Examples of the compound having an alkyl group include various polymer compounds containing a long-chain alkyl group, amine compounds containing a long-chain alkyl group, ether compounds containing a long-chain alkyl group, and quaternary ammonium salts containing a long-chain alkyl group. Considering heat resistance and contamination, a polymer compound is preferred. From the viewpoint of obtaining a significant and appropriate water repellency with a small content, a polymer compound having a long-chain alkyl group in a branched chain is preferred.

The polymer compound having a branched long-chain alkyl group may be, for example, a (meth) acrylic polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer containing an alkyl group having 6 or more carbon atoms, and A polymer obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Examples of the compound having the reactive group include polyvinyl alcohol, butyraldehyde resin, ethylene-vinyl alcohol resin, polyethyleneimine, polyvinylamine, a polyester resin containing a reactive group, and a polymer containing a reactive group. (Meth) acrylic resin and the like. In view of mold releasability and ease of handling, among these, (meth) acrylic polymers, polyvinyl alcohol, butyraldehyde resin, and ethylene-vinyl alcohol resin are preferred.

<(Meth) acrylic polymer containing an alkyl group having 6 or more carbon atoms>

Monomer containing a (meth) acrylic monomer containing an alkyl group having 6 or more carbon atoms The (meth) acrylic polymer formed by polymerizing the components should preferably contain a (meth) acrylic monomer containing an alkyl group having 6 or more carbon atoms relative to the total amount of monomer components constituting the (meth) acrylic polymer. The body is 10 to 80% by weight, preferably 20 to 70% by weight, more preferably 30 to 70% by weight, and most preferably 30 to 60% by weight. By being in this range, the obtained release layer has excellent light peelability to the adhesive layer.

As the polymerizable monomer other than the (meth) acrylic monomer having an alkyl group having 6 or more carbon atoms, for example, a hydroxyl-containing (meth) acrylic monomer and a carboxyl-containing (meth) group are suitably used. Acrylic monomers, cyano-containing monomers, vinyl ester monomers, aromatic vinyl monomers, fluorenamine-containing monomers, fluorenimine-containing monomers, amine-containing monomers, epoxy-containing monomers Monomers, N-acrylfluorenyl morpholine, vinyl ether monomers, and the like. These polymerizable monomers may be used alone or in combination of two or more.

Among them, it is preferable to use a carboxyl group-containing (meth) acrylic monomer and a cyano group-containing monomer from the viewpoint of excellent light peelability to the adhesive layer and adhesion to the substrate. Examples of the carboxyl group-containing (meth) acrylic monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acryloxy Ethylhexahydrophthalate, 2- (meth) acryloxypropylhexahydrophthalate, 2- (meth) acryloxyethyl phthalate, 2- (meth) acryl Oxyethyl succinate, 2- (meth) acryloxyethylmaleate, carboxypoly (ca) lactone mono (meth) acrylate, 2- (meth) acryloxyethyl tetra Hydrophthalates and the like. Examples include acrylonitrile and methacrylonitrile. Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

<Polymer obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group>

Examples of the compound having an alkyl group capable of reacting with the reactive group include octyl isocyanate, decyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, and behenyl isocyanate. Isocyanates; chlorooctane, chlorodecane, chlorododecane, chlorooctadecane, chloro behenane, and other sulfonium chlorides containing long chain alkyl groups; amines containing long chain alkyl groups, and Alcohol and so on. Among them, considering release properties and ease of handling, an isocyanate containing a long-chain alkyl group is preferred, and an octadecyl isocyanate is particularly preferred.

With respect to 100 parts by weight of the polymer having a reactive group, the compound having an alkyl group capable of reacting with the reactive group is preferably used in a reaction of 100 to 1,000 parts by weight, more preferably 200 to 800 parts by weight, and more preferably 300 ~ 700 parts by weight. If it is within this range, light peelability to the adhesive layer and contamination of the adhesive layer by the optical surface protective film can be suppressed, which is preferable.

<Aliphatic carboxylic acid ester>

The aliphatic carboxylic acid ester can be obtained by reacting an aliphatic carboxylic acid with an alcohol. As the aforementioned aliphatic carboxylic acid component, a mono- or dicarboxylic acid having 6 to 36 carbon atoms is preferable, and an aliphatic saturated monocarboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such an aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, hexanoic acid, capric acid, dodecanoic acid, icosanoic acid, behenic acid, behenic acid, and icos Hexanoic acid, tricosalic acid, triconic acid, octacosanoic acid, glutaric acid, adipic acid, azelaic acid, etc.

On the other hand, examples of the alcohol include a saturated or unsaturated monovalent alcohol, a saturated or unsaturated polyvalent alcohol, and the like. These alcohols may have a substituent such as a fluorine atom and an aromatic group. Among these alcohols, monovalent or polyvalent saturated alcohols having a carbon number of 30 or less are preferred, and aliphatic saturated monovalent or polyvalent alcohols having a carbon number of 30 or less are more preferred good. Aliphatic alcohols here also include alicyclic alcohols. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, eicosanediol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, and 2,2-diol. Hydroxyperfluoropropanol, neopentyl glycol, bistrimethylolpropane, dipentaerythritol, etc. These aliphatic carboxylic acid esters may also contain an aliphatic carboxylic acid and / or an alcohol as impurities, and may also be a mixture of plural compounds.

Specific examples of the aforementioned aliphatic carboxylic acid esters include beeswax (a mixture containing beesyl palmitate as a main component), stearyl stearate, behenyl behenate, and octyl Dodecyl behenate, glyceryl monomelate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monomelate, pentaerythritol monostearate , Pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate.

The carboxylic acid ester is preferably contained in the release agent composition in an amount of 70 to 99% by weight, more preferably 80 to 99% by weight, and more preferably 90 to 99% by weight. If it is within this range, it is preferable because it has excellent light peelability to the adhesive layer.

In addition, the aforementioned release agent composition may also contain other well-known additives, for example, powders such as antistatic agents, colorants, and pigments, surfactants, plasticizers, adhesion-imparting agents, and Molecular weight polymers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, particles, etc.

<Making of partitions>

The separator is formed by using the release agent composition on the substrate.

The method for forming a release layer on a substrate is not particularly limited. For example, a solution of the aforementioned release agent composition is applied to a substrate, and a polymerization solvent is dried and removed to form a release agent layer on the substrate. Production. After that, it is also possible to carry out curing for the purpose of adjusting and transferring the components of the release layer. When the release agent composition is coated on a substrate to prepare a release layer, one or more solvents other than a polymerization solvent may be added to the release agent composition to uniformly apply the release agent composition. On the substrate.

As a method for forming the release layer, a known method for producing a release layer can be used. Specifically, for example, roll coating, gravure coating, reverse coating, roll brush coating, spray cloth, pneumatic blade coating method, squeeze coating method of a slit coater, and the like can be mentioned.

The thickness of the aforementioned release layer is typically 1 to 200 nm, preferably 5 to 100 nm, and more preferably 10 to 50 nm. If the thickness of the release layer is too small, it may be difficult to peel off the separator. Therefore, it may be difficult to apply the surface protective film for optical applications. On the other hand, if it is too thick, the contamination of the adhesive layer of the optical surface protection film may be affected.

<Lamination of Optical Surface Protective Film and Separator>

The optical surface protective film with a separator according to the present invention has a form in which the adhesive layer of the aforementioned optical surface protective film is bonded to the release layer of the aforementioned separator. The sticking industry can use well-known manufacturing methods.

<Measurement of Si-Kα line intensity under fluorescent X-ray>

In the optical surface protective film with a separator of the present invention, after the aforementioned separator adhered to the optical surface protective film is peeled off, the intensity of the Si-Kα line of the surface of the adhesive layer under fluorescent X-rays can be reduced. Measured adhesive layer The amount of silicon atoms on the surface. The intensity of the Si-Kα line of the surface of the adhesive layer under fluorescent X-rays is 2.5 kcps or less, preferably 2.4 or less, more preferably 2.2 or less, and most preferably 2.0 or less. If it is within this range, the surface protective film for optical separation of the separator is adhered to the adherend (for example, a glass plate), and then it is peeled off, which can affect the surface contamination of the adherend caused by the adhesive layer. Smaller (can suppress, for example, the release of an organopolysiloxane such as polydimethylsiloxane from a release layer of a separator to improve peelability, due to the adhesion of the separator to an optical surface protective film To the surface of the adhesive layer, the transferred organic polysiloxane is transferred to the adherend), so it is preferred. As a result, peeling of other layers such as the interlayer filler (layer) provided on the adherend can be prevented.

<Measurement of difference in peeling force of adhesive tape>

The influence on the contamination on the surface of the aforementioned adhesive body can be measured from the difference in the peeling force of the adhesive tape. The difference in the peeling force of the adhesive tape can be obtained by the formula (1): The difference in the peeling force of the adhesive tape (N / 50mm) = F ₀ -F (N / 50mm).

Here, F means that the optical surface protection film with the separator peeled off was attached to a glass plate of an adherend, and after being heated at 70 ° C. for 48 hours, and after being left at room temperature for 1 hour, the optical surface protection film was peeled off. , On the surface of the glass plate to which the surface protection film for optical application was originally attached, a single-sided adhesive tape manufactured by Nitto Denko Corporation with a product number "No. 31B" (width 19 mm) was used at a temperature of 23 ° C and 50% RH. After 20 minutes under the conditions, the peeling force (N / 19mm) of the adhesive tape peeled at a peeling angle of 180 ° and a tensile speed of 0.3m / min was converted into a peeling force (N / 50mm) of a measured value of 50mm in width. .

F ₀ means that the optical surface protection film is not bonded to the glass plate, and a 2 kg roller is directly bonded to the surface of the glass plate. Nitto Denko Co., Ltd. single-sided adhesive tape product number "No. 31B", at 23 ° C After 20 minutes at 50% RH, the peeling force (N / 19mm) of the adhesive tape that was peeled at a peeling angle of 180 ° and a tensile speed of 0.3m / min was converted into a peeling force of 50mm in width ( N / 50mm).

The difference in the peeling force of the adhesive tape can be used as an indicator of the adhesion of other layers (for example, interlayer fillers (layers)) provided on the optical component after the optical surface protective film is peeled off, thereby making it possible to adhere to the adhesive tape. The degree of contamination on the body surface was evaluated.

The difference in the peeling force of the aforementioned adhesive tape is preferably 4.0 N / 50 mm or less, more preferably 3.6 N / 50 mm or less, even more preferably 3.2 N / mm or less, and most preferably 2.8 or less. Within this range, the effect of the adhesive layer on contamination of the surface of the adherend after peeling off the optical surface protection film is reduced, and it is possible to prevent other layers such as the interlayer filler (layer) provided on the adherend from peeling off.

<Measurement of peeling force of separator on optical surface protection film>

Regarding the optical surface protective film with a separator of the present invention, the optical surface protective film is bonded to the separator, and after being left for 20 minutes under the conditions of 23 ° C and 50% RH, the peeling angle is 180 ° and the peeling speed is 0.3. It can be peeled under the condition of m / min, and the peeling force of the separator to the optical surface protective film can be obtained. The peeling force of the separator on the optical surface protection film is 0.5N / 50mm or less, preferably 0.4N / 50mm or less, more preferably 0.3N / 50mm or less, more preferably 0.2N / 50mm or less, and most preferably 0.1N / 50mm or less. It is more preferably 0.03N / 50mm or more, more preferably 0.05N / 50mm or more, and still more preferably 0.08N / 50mm or more. If it is within this range, the adhesive layer can be formed. A separator having excellent peelability and excellent workability during bonding.

<Measurement of Peel Force of Glass Surface Protective Film to Glass>

Regarding the optical surface protective film with a separator according to the present invention, the optical surface protective film with the separator peeled off was attached to the surface of a glass plate using a 2 kg roller, and 20 minutes passed at 23 ° C and 50% RH. Then, peeling was performed under the conditions of a peeling angle of 180 ° and a stretching speed of 0.3 m / min, and the peeling force of the surface protective film for optics from glass was obtained. The peeling force of the aforementioned surface protective film for glass on the glass is 0.08N / 25mm or less, preferably 0.07N / 25mm or less, preferably 0.06N / 25mm or less, more preferably 0.05N / 25mm or less, and most preferably 0.04N / 25mm or less. It is more preferably 0.01N / 25mm or more, more preferably 0.02N / 25mm or more, and still more preferably 0.03N / 25mm or more. Within this range, an adhesive layer having excellent peelability to an adherend such as glass can be formed.

<Determination of silicon atomic element ratio by X-ray photoelectron spectroscopy (ESCA)>

Regarding the optical surface protective film with a separator of the present invention, the surface of the adhesive layer after peeling off the aforementioned separator bonded to the optical surface protective film is measured using X-ray photoelectron spectroscopy, and the adhesive layer can be calculated. The atomic percentage of the topmost silicon atom (Si). The element ratio (atomic%) of the silicon atom (Si) on the outermost surface of the adhesive layer is preferably 0.5 or less, more preferably 0.3 or less, and most preferably 0.2 or less. If it is within this range, the surface protective film for optical with the separator peeled off is adhered to the adherend (for example, a glass plate) and then peeled off. Reduced influence (can suppress, for example, the organic silicon oxidation of polydimethylsiloxane included in the release layer of the separator to improve peelability It is preferred that it is transferred to the surface of the adhesive layer due to the attachment of the separator and the optical surface protective film, and the transferred organic polysiloxane is transferred to the adhesive body), so it is preferable. As a result, peeling of other layers such as the interlayer filler (layer) provided on the adherend can be prevented.

The peeling of the aforementioned optical surface protection film of the present invention and the other layers provided on the adherend may be, for example, interlayer fillers (layers). The above-mentioned interlayer filler (layer) is, for example, filled between the cover glass and the liquid crystal panel and used for the purpose of improving visibility. Specifically, SVR7000 series, SVR1120, SVR1150, SVR1320, and SVR1241H Company) and WORLD ROCK 700 series, WORLD ROCK801, A-350 series, WORLD ROCK HRJ-40, HRJ-203, HRJ-300, HRJ-302 (made by Kyoritsu Chemical Industry Co., Ltd.) and so on.

[Example]

Hereinafter, examples and the like which specifically show the constitution and effects of the present invention will be described, but the present invention is not limited by these. The evaluation items of the examples and the like were measured as follows.

<Example 1>

<Preparation of (meth) acrylic polymer (A1)>

A four-necked flask equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooling device was charged with 100 parts by weight of 2-ethylhexyl acrylate (2EHA, manufactured by Toa Synthesis, 2-ethylhexyl acrylate), 2- 4 parts by weight of hydroxyethyl acrylate (HEA, manufactured by Toya Synthesis, ACRYCS HEA), 0.2 parts by weight of 2,2'-azobisisobutyronitrile (Wako Pure Chemical Industries, AIBN) as a polymerization initiator, ethyl acetate (Showa Denko, ethyl acetate) 205 parts by weight, gently stirring Nitrogen was introduced while stirring, and the temperature of the liquid in the flask was maintained at about 63 ° C. and a polymerization reaction was performed for about 4 hours to prepare a (meth) acrylic polymer (Al) solution (about 35% by weight). The weight average molecular weight of the (meth) acrylic polymer (A1) was 650,000, and Tg was -68.3 ° C.

<Preparation of Adhesive Composition>

The aforementioned (meth) acrylic polymer (A1) solution (about 35% by weight) was diluted to 29% by weight with ethyl acetate, and 100% by weight (solid content) of the (meth) acrylic polymer based on this solution 4 parts by weight of an isocyanurate body (Coronate HX, manufactured by Japan Polyurethane Industry Co., Ltd.) of hexamethylene diisocyanate, and tin octyldodecanoate (made by Tokyo Fine Chemical, EMBILIZER OL) as a tin-based catalyst -1) 0.015 parts by weight, 0.69 parts by weight of acetone and acetone, which is a compound capable of generating keto-enol interdenaturation, was maintained at about 25 ° C., and the mixture was stirred for about 1 minute to prepare an adhesive composition (1).

<Production of Separator A>

100 parts by weight of a resin obtained after drying of a butyraldehyde resin (manufactured by Sekisui Chemical Industry, S-LEC KW-10) was dissolved in 900 parts by weight of xylene (manufactured by Sun Chemical, xylene), and then octadecyl isocyanate (Ohara Paragium) was added. Chemical Co., Ltd., R-NCO) 480 parts by weight. This solution was then diluted with toluene (manufactured by Idemitsu Petrochemical) to a solid content of 0.3% by weight to obtain a release agent composition. This release agent composition was applied to a PET film (diafoil T100C38, manufactured by Mitsubishi Resin) having a thickness of 38 μm, and dried at 130 ° C. for 1 minute to prepare a separator A. The thickness of the release layer after drying was 20 nm.

<Production of Optical Surface Protection Film with Separator>

The above-mentioned adhesive composition (1) was applied to a PET substrate (made by Mitsubishi resin, Diafoil T100C38 (thickness: 38 μm), heated at 130 ° C. for 60 seconds to form an adhesive layer with a thickness of 10 μm to produce an optical surface protection film. Next, the release layer of the separator A was bonded to the surface of the aforementioned adhesive layer using a hand roller to produce a surface protective film for an optical with a separator. In addition, when attaching to an adherend (use), the aforementioned separator is removed and used.

<Production of Separator B>

A reaction vessel equipped with a cooler was charged with 100 parts by weight of acrylonitrile (acrylonitrile, manufactured by Showa Denko Corporation), 62.5 parts by weight of stearyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., SMA), and methacrylic acid ( 18 parts by weight of Mitsubishi Rayon Co., Ltd., methacrylic acid), 1.8 parts by weight of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd., 1-dodecyl mercaptan), 1.8 parts by weight of benzamidine peroxide (manufactured by Nippon Oil Co., Ltd.) (Nyper BW), 0.55 parts by weight, diluted with toluene (manufactured by Idemitsu Petrochemical) to 24% by weight, and reacted at 70 ° C. for 7 hours under a nitrogen stream. The obtained liquid was diluted with toluene to 0.3% by weight, and a mold release agent composition was obtained. Then, a separator B was prepared in the same manner as the separator A.

<Production of Separator C>

Toyobo's Toyobo Ester Film TN101 (thickness: 38 μm) was used. The release layer constituting the separator C is formed of a release agent composition containing a pentaerythritol fatty acid ester.

<Production of Separator D>

In a reaction vessel equipped with a cooler, 200 parts by weight of xylene (manufactured by Taiko Chemical, xylene) and 600 parts by weight of octadecyl isocyanate (R-NCO manufactured by Ohara Paragium Chemical Co., Ltd.) were added. When xylene started to reflux, polyvinyl alcohol (made by Kuraray, KURARAY POVAL 205) 100 parts by weight are added in small portions so that it takes 2 hours and each interval is 10 minutes. After completion of the polyvinyl alcohol addition, it took another 2 hours to reflux, and the reaction was completed. The reaction mixture was cooled to about 80 ° C and then added to methanol to precipitate a white precipitate as a reaction product. This precipitate was separated by filtration, 140 parts by weight of xylene was added, and it was heated to completely dissolve. Then, methanol was added again and precipitated. After repeating this operation several times, the precipitate was washed with methanol, and the powder obtained after drying and pulverization was diluted with water to 0.3% by weight. Using the obtained solution, a separator D was produced in the same manner as in the separator A.

<Divider E>

A Fuji binary 50E-0010NSD (50 μm thickness) was used. The release layer constituting the separator E is formed of a release agent composition containing a pentaerythritol fatty acid ester.

<Divider F>

100 parts by weight of a polysiloxane release agent (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847H) and 3.3 parts by weight of a polysiloxane curing catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) were added. Toluene (manufactured by Idemitsu Petrochemical Co., Ltd.) was used. ), Hexane (manufactured by Maruzen Petrochemical, Normal hexane), methyl ethyl ketone (produced by Idemitsu Kogyo, MEK) at a weight ratio of 1: 2: 1, and the solvent formed was diluted to 0.3% by weight to obtain a release agent.组合 物。 Composition. Using the obtained release agent composition, a separator F was produced in the same manner as the separator A.

<Examples 2 to 8, Comparative Examples 1 to 3, and blank control group 1>

As shown in Tables 1 and 2, except that the monomer components constituting the (meth) acrylic polymer and the treatment of the separator described above were changed, it was the same as in Example 1. The optical surface protective films with separators of Examples 2 to 8 and Comparative Examples 1 to 3 were prepared by the method described above. As a blank control group 1, an optical surface protective film without a separator was produced. In addition, as an iron catalyst, ginseng (acetone) iron (trade name "Nasemu second iron" manufactured by Japan Chemical Industry Co., Ltd.) was used.

<Measurement. Evaluation>

The following describes specific blending amounts and measurements. The evaluation methods are described in Tables 1 and 2.

<Measurement of weight average molecular weight (Mw) of (meth) acrylic polymer (A)>

The weight average molecular weight of the produced polymer was measured using GPC (gel permeation chromatography). The conditions are as follows.

Device: TOSOH company, HLC-8220GPC

Sample column; manufactured by TOSOH, TSKguardcolumn Super HZ-H (1) + TSKgel Super HZM-H (2)

Reference column; manufactured by TOSOH, TSKgel Super H-RC (1)

Flow: 0.6ml / min

Injection volume: 10 μl

Column temperature: 40 ℃

Eluent: THF

Injection sample concentration: 0.2% by weight

Detector: Differential refractometer

The weight-average molecular weight is determined in terms of polyethylene.

<Glass transition temperature (Tg) of (meth) acrylic polymer (A) The determination>

The glass transition temperature (Tg) (° C) is a value of the following literature using the glass transition temperature Tgn (° C) of the homopolymer of each monomer, and is determined by the following formula.

Formula: 1 / (Tg + 273) = Σ [Wn / (Tgn + 273)]

(In the formula, Tg (° C) is the glass transition temperature of the copolymer, Wn (-) is the weight fraction of each monomer, Tgn (° C) is the glass transition temperature of the homopolymer of each monomer, and n is each The type of monomer.)

2-ethylhexyl acrylate (2EHA): -70 ° C

Hydroxyethyl acrylate (HEA): -15 ° C

4-hydroxybutyl acrylate (HBA): -32 ° C

Acrylic (AA): 106 ° C

In addition, as the document value, refer to "Synthesis, Design, and New Application Development of Acrylic Resin" (published by the Publishing Department of the Central Management Development Center).

<Measurement of Si-Kα line strength>

After separating the separator from the obtained optical surface protective film with a separator, the Si-Kα line strength of the surface of the adhesive layer of the optical surface protective film under fluorescent X-rays was used to measure the adhesive under the following conditions The amount of silicon atoms on the surface of the layer.

Device: XRF ZSX100e by Rigaku

X-ray source: vertical Rh tube

Analysis area: 30mmφ

Analysis element: Si

Spectroscopic crystal: RX4

Output: 50kv, 70mA

The sample (area = 30mmφ) was irradiated with excited X-rays (ray source = vertical Rh tube, output = 50kv, 70mA), and the intensity of the fluorescent X-ray of the spectroscopic Si was measured with a spectroscopic crystal (= RX4).

In addition, the surface of the adhesive layer of the optical surface protective film (blank control group 1) without using a separator was also subjected to the above conditions to measure the Si-Kα line intensity under fluorescent X-rays. As a result, the silicon atoms of the polyester film and the substrate (for example, silicon dioxide (SiO2 as a filler in PET film) (SiO2) in the PET film and the substrate were detected without using a silicone material for the adhesive layer or the release layer with respect to the aforementioned silicon atomic weight. ₂ )), the Si-Kα line strength is not 0kcps, and the adhesive layer of the optical surface protection film (blank control group 1) without a separator is 1.9kcps.

The Si-Kα line strength on the surface of the adhesive layer after peeling the separator is preferably 2.5 kcps. Within this range, after the optical surface protection film from which the separator is peeled is peeled from the glass plate, the influence of the surface contamination of the glass plate by the adhesive layer becomes small (for example, it can be suppressed in the release layer of the separator). The organic polysiloxane containing polydimethylsiloxane such as polydimethylsiloxane is transferred to the surface of the adhesive layer due to the adhesion of the separator and the optical surface protective film. The transferred organic polysiloxane It is then transferred to the adherend), so that other layers such as the interlayer filler (layer) can be prevented from peeling from the adherend.

<Measurement of difference in peeling force of adhesive tape>

The obtained optical surface protective film with a separator was peeled off, and the glass sheet (Matsulang Glass, made of green plate edge grinding OF1) was bonded to the glass surface, and then heated in an oven at 70 ° C. for 48 hours. Take it out of the oven and leave it at room temperature for 1 hour to peel off the optical surface protection film, and attach the optical surface protection to the original The surface of the film was laminated with an acrylic adhesive tape (manufactured by Nitto Denko, No. 31B, 19 mm in width) using a 2 kg roller, and left for about 20 minutes at 23 ° C and 50% relative humidity. The peeling force was measured at a speed of 0.3 m / min and an angle of 180 °, and the peeling force was measured and converted into a measured value of 50 mm in width. This was taken as the F value of the following formula (1).

In addition, the optical surface protection film was not bonded to a glass plate, and No. 31B was directly bonded to the glass plate, and the peeling force was similarly measured. The measured value was converted into a measurement value of 50 mm in width, and this was defined as F in the following formula (1) ₀ value. At this time, the peeling force of No. 31B was 18.7 N / 50 mm.

Next, the difference of the peeling force of these adhesive tapes was calculated by following formula (1).

Formula (1): Difference of peeling force of adhesive tape (N / 50mm) = F ₀ -F (N / 50mm)

The difference in the peeling force of the adhesive tape is preferably 4.0 N / 50 mm or less. The smaller this value is, the smaller the effect of glass surface contamination caused by the adhesive layer after peeling the optical surface protection film is. For example, it is possible to prevent other layers such as interlayer fillers (layers) provided on the glass surface from peeling.

<Measurement of peeling force of separator on optical surface protection film>

The obtained optical surface protective film with a separator was cut into a width of 50 mm, and the opposite surface (polyester film) of the surface to which the adhesive layer was attached was fixed to a SUS board (SUS304BA). After being left in an environment of 23 ° C. and a relative humidity of 50% for about 20 minutes, it was peeled off at a speed of 0.3 m / min and an angle of 180 °, and the peeling force (N / 50 mm) of the separator to the optical surface protective film was measured.

The peeling force of the separator on the optical surface protection film is 0.5N / 50mm is preferred. If it is in this range, it can become a separator which is excellent in the peelability with respect to the said adhesive layer, and is excellent in the workability | operativity at the time of bonding.

<Evaluation of separator peelability>

Regarding the evaluation of the peelability of the separator, a case where the peeling force of the separator to the optical surface protective film is 0.5 N / 50 mm or less is regarded as good ((), and a case where the peel force is larger than 0.5 N / 50 mm is regarded as bad (╳).

<Measurement of Peel Force of Glass Surface Protective Film to Glass>

The obtained optical surface protective film with a separator was cut into a width of 25 mm, the separator was peeled off, and the glass plate (Matsulang Glass, Green Plate Edge Grinding Product, OF1) was laminated with a 2 kg roller, and the relative temperature was 23 ° C. Leave it for about 20 minutes in a 50% humidity environment. The surface protective film for optics was peeled at a speed of 0.3 m / min and an angle of 180 °, and the peeling force (N / 25 mm) of the surface protective film for optics to glass was measured.

The peeling force of the aforementioned surface protective film for glass on glass is preferably 0.08 N / 25 mm or less. If it exists in this range, it can become the optical surface protection film which has an adhesive layer which is excellent in the peelability with respect to glass, such as an adherend.

<Determination of silicon atomic element ratio by X-ray photoelectron spectroscopy (ESCA)>

After separating the separator from the obtained optical surface protective film with a separator, the surface of the adhesive layer was measured by X-ray photoelectron spectroscopy, and the element ratio of silicon atoms (Si) on the outermost surface of the adhesive layer was calculated under the following conditions.

Installation: ULVAC PHI, PHI Quantera SXM

X-ray source: monochrome AlKα

X-ray setting: 100μmφ [15kV, 25W]

Photoelectron grazing angle: 45 ° relative to the sample surface

The obtained optical surface protective film with a separator was appropriately cut, and measured by X-ray photoelectron spectroscopy to calculate an atomic percentage of silicon atoms.

The silicon atomic element ratio is preferably 0.5 atomic% or less. Within this range, the effect of contamination of the glass surface caused by the adhesive layer after the separation of the optical surface protection film from which the separator is peeled from the glass plate is reduced (for example, it can be suppressed from being contained in the release layer of the separator). In order to improve the peelability, an organic polysiloxane such as polydimethylsiloxane is transferred to the surface of the adhesive layer due to the adhesion of the separator and the optical surface protective film. The transferred organic polysiloxane is then transferred to the surface of the adhesive layer. Being transferred to the adherend), it is possible to prevent other layers such as the interlayer filler (layer) from being peeled from the adherend.

<Determination of the Si-Kα line intensity difference between the surface of the release layer of the separator and the surface of the substrate of the separator under fluorescent X-rays>

According to the above conditions for measuring the Si-Kα line strength, measure the Si-Kα line strength (a) of the release layer surface of the separator under fluorescent X-rays, and the surface of the substrate without the release layer (not Treatment surface) Si-Kα line intensity (b) under fluorescent X-rays, and the difference [(b)-(a)] was determined. As a result, the aforementioned Si-Kα linear strength (a) of the separator C was 3.78 kcps, and the aforementioned Si-Kα linear strength (b) of the separator C was 3.98 kcps, and the difference [(b)-(a)] thereof was 0.20. kcps. In addition, the aforementioned Si-Kα linear strength (a) of the separator E is 6.52 kcps, and the aforementioned Si-Kα linear strength (b) of the separator E is 6.73 kcps, and the difference [(b)-(a)] thereof is 0.21 kcps. . In addition, divider F The aforementioned Si-Kα linear strength (a) is 75.5 kcps, the aforementioned Si-Kα linear strength (b) of the separator F is 7.36 kcps, and the difference [(b)-(a)] thereof is 68.14 kcps.

From the results in Table 2 above, it was confirmed that the Si-Kα line strength in all the examples was less than 2.5 kcps, so that the stain resistance was excellent. In addition, it was confirmed that the peeling force of the separator from the optical surface protective film was 0.5 N / 50mm or less, excellent workability during bonding. In contrast, it was confirmed that in Comparative Examples 1 and 3, the Si-Kα line strength was greater than 2.5 kcps; in Comparative Example 2, the peeling force of the separator to the adhesive layer was greater than 0.5 N / 50 mm; Comparative Examples 1 to 3 Compared to the examples, the performance of these is inferior.

In addition, from the results in Table 2 above, it was confirmed that the difference in the peeling force of the adhesive tape in all the examples was 4.0 N / 50 mm or less. Therefore, the influence of the surface contamination of the glass caused by the adhesive layer after the optical surface protective film was peeled off. It is small, so that other layers such as interlayer fillers (layers) can be prevented from peeling off. In addition, the surface protective film has a peeling force of 0.08N / 25mm or less on the glass, so it has excellent peelability on glass. In addition, it has good separator peelability. In addition, it was confirmed that the element ratio of silicon atoms (Si) on the outermost surface of the adhesive layer was 0.5 atomic% or less, and thus excellent in stain resistance. On the other hand, in Comparative Examples 1 and 3, it was confirmed that the difference in the peeling force of the adhesive tape was larger than 4.0N / 50mm. In addition, the silicon atomic element ratio on the outermost surface of the adhesive layer was 2.0 atomic% or more; Comparative Example Among the two, the peeling force of the optical surface protection film on the glass is larger than 0.08N / 25mm, and the separator has poor peelability; Comparative Examples 1 to 3 have lower and inferior properties than Examples.

Claims (6)

An optical surface protection film with a separator is a polyester film on one side of an adhesive layer and a separator on the side of the adhesive layer opposite to the polyester film, characterized in that the separator has The release layer and the substrate, and the thickness of the release layer is 1 to 200 nm; the intensity of the Si-Kα line under fluorescent X-rays of the surface of the adhesive layer after the separator is peeled is 2.5 kcps or less; the foregoing separation The peeling force of the piece to the optical surface protection film is 0.5 N / 50 mm or less at a tensile speed of 0.3 m / minute. The optical surface protective film with a separator according to claim 1, wherein the release layer is formed of a release agent composition containing a long-chain alkyl-based material and / or an aliphatic carboxylic acid ester. For example, the optical surface protective film with a separator in claim 1 or 2, wherein the aforementioned adhesive layer is adhered by a (meth) acrylic polymer (A) and an aliphatic polyisocyanate-based crosslinking agent (B). Agent composition; the (meth) acrylic polymer (A) contains at least a (meth) acrylic monomer having a carbon number of 2 to 14 alkyl groups and a hydroxyl group-containing (meth) acrylic monomer as Monomer component with a glass transition temperature of -50 ° C or lower; and 100 parts by weight of the (meth) acrylic monomer having 2 to 14 alkyl groups and containing the hydroxyl group-containing (meth) acrylic acid The monomer is 2 to 20 parts by weight. For example, the optical surface protective film with a separator according to claim 3, which contains 1 to 30 parts of the aliphatic polyisocyanate-based crosslinking agent (B) with respect to 100 parts by weight of the (meth) acrylic polymer (A). Parts by weight. For example, the optical surface protective film with a separator in claim 3, wherein the aforementioned adhesive composition further contains a catalyst (C) with iron or tin as an active center. For example, the optical surface protective film with a separator according to claim 5, which contains 0.002 of the aforementioned catalyst (C) with iron or tin as the active center based on 100 parts by weight of the (meth) acrylic polymer (A). ~ 0.5 parts by weight.