KR102429401B1 - Resin composition dispersed in water, highly adhesive film and manufacturing method of resin composition - Google Patents

Abstract

The water-dispersible resin composition contains a (meth)acrylic resin and a polyester resin, and the (meth)acrylic resin includes a structural unit derived from a vinyl-based monomer having an aryl group, and the aryl based on the total mass of the total structural unit. The content rate of the structural unit derived from the vinylic monomer having a group is 60 mass % or more, It is obtained by polymerizing the monomer which comprises the said (meth)acrylic resin in presence of the said polyester resin and an aqueous medium.

Description

A water-dispersible resin composition, an easily adhesive film, and a method for producing a water-dispersible resin composition TECHNICAL FIELD

The present invention relates to a water-dispersible resin composition, an easily adhesive film, and a method for preparing a water-dispersible resin composition.

Optical components such as liquid crystal displays and touch panels are laminated with a plurality of optical films having different functions. For example, in optical films such as prism sheets and hard coat films, a layer (functional layer) having a certain function is further formed on a transparent resin film such as a polyethylene terephthalate (PET) film serving as a base material. have. PET film, which is generally used as a base material for optical films, has low easy adhesion to functional layers. Therefore, in order to improve the adhesiveness of the functional layer with respect to a base material, an optical film has an easily adhesive layer between a base material and a functional layer in many cases.

These optical films are manufactured by laminating a functional layer on an easily adhesive film in which an easily adhesive layer is formed on a base material.

The easily adhesive layer is formed using a resin composition containing (meth)acrylic resin, polyester resin, polyurethane resin, etc. as a main component. It is known that the easily adhesive layer has different easily adhesive properties for the functional layer depending on the resin component included in the resin composition used to form the easily adhesive layer. For example, it is known that an easily adhesive layer formed of a resin composition including a (meth)acrylic resin exhibits excellent easy adhesion to a layer having a high hardness, such as a hard coat layer formed of a UV curing (meth)acrylic resin. In addition, the easily adhesive layer formed by the resin composition including the polyester resin has excellent easy adhesion to the PET film as the base material, and furthermore, a layer with high elasticity and flexibility, such as a prism layer formed of a solvent-free UV-curing urethane acrylate-based resin. It is known that it exhibits excellent easy adhesion to the .

Moreover, in general, the hard-coat layer is requested|required of the hardness to the extent to which it is hard to be damaged in many cases. Moreover, in general, the prism layer is easily peeled from a manufacturing type|mold, and it is calculated|required that it can exhibit a light-collecting effect in many cases.

For example, Japanese Patent Application Laid-Open No. 2010-53227 discloses an aqueous dispersion of an acrylic copolymer containing an acrylic resin as a main component as a resin component capable of forming an easily adhesive layer with good easy adhesion to the hard coat layer.

In addition, it is known that, in an optical film having an easily adhesive layer, when the refractive index of the easily adhesive layer is significantly different from the refractive index of the other layers, iris-shaped reflected light is easily generated and visibility is easily deteriorated.

For example, in Japanese Patent Application Laid-Open No. 2012-187823, a polyester resin having a fluorene skeleton or a naphthalene skeleton as an optically easy-to-adhesive film excellent in suppression of interference fringes when used as a base material for an optical hard coat film (meta ) Disclosed is a polyester film coated with a water-based coating composition including an acrylic polymer.

For example, the water-based coating composition described in Japanese Patent Application Laid-Open No. 2012-187823 is a resin composition of a so-called blend type in which a (meth)acrylic polymer and a polyester resin are separately polymerized and then each resin is mixed (hereinafter, “blend”) resin composition") is being prepared. Blended resin compositions containing resins of different properties tend to be easily phase-separated after application to a base material or the like. In the case of using such a blend resin composition, since the easily adhesive properties of the easily adhesive film change depending on the degree of phase separation, the functional layer that can be formed is limited, and it was necessary to prepare an easily adhesive film tailored to the functional layer.

In addition, for example, the easily adhesive film formed of the acrylic resin described in Japanese Patent Application Laid-Open No. 2010-53227 may have poor easy adhesion to a layer having high elasticity and flexibility, such as a prism layer.

A transparent resin film, such as a PET film, which is widely used as a base material, has a refractive index of about 1.61 to 1.63, and a functional layer such as a hard coat layer has a refractive index of about 1.56 to 1.60. The refractive index of the easily adhesive layer formed of (meth)acrylic resin is about 1.48 to 1.50, which is lower than that of the base material and the functional layer. Therefore, it is required to increase the refractive index of the easily adhesive layer formed of (meth)acrylic resin to about 1.56 to 1.63 and to reduce the generation of iris-shaped reflected light.

The present invention has been made in view of the above, and is excellent in easy adhesion to both the functional layer and the base material regardless of the material of the applied functional layer, and is capable of suppressing the generation of iris-shaped reflected light, a water-dispersible composition, an easily adhesive film, and moisture A method for producing an acid-type resin composition is provided.

The present invention includes the following aspects.

<1> contains a (meth)acrylic resin and a polyester resin, the (meth)acrylic resin includes a structural unit derived from a vinyl-based monomer having an aryl group, and has the aryl group relative to the total mass of all structural units It is a water dispersion type resin composition obtained by polymerizing the monomer which comprises the said (meth)acrylic resin in the presence of the said polyester resin and an aqueous medium, and the content rate of the structural unit derived from a vinylic monomer is 60 mass % or more.

<2> The said polyester resin is the water dispersion type resin composition as described in <1> which has a naphthalene skeleton.

<3> The content ratio of the (meth)acrylic resin to the polyester resin is 30/70 to 90/10 by mass, the water dispersion type resin composition according to <1> or <2>.

<4> The water-dispersible resin composition according to any one of <1> to <3>, wherein the polyester resin has a weight average molecular weight of 5,000 to 100,000.

<5> The polyester resin is a water-dispersible resin composition according to any one of <1> to <4>, wherein the polyester resin is water-soluble or water-dispersible.

<6> The (meth)acrylic resin further includes a structural unit derived from a monomer having a carboxyl group and a structural unit derived from a monomer having a methylol group, and the monomer having a carboxyl group with respect to the total mass of all structural units. The content rate of the structural unit derived from 0.5 mass % to 15 mass %, and the content rate of the structural unit derived from the monomer which has the said methylol group with respect to the total mass of all structural units is 0.5 mass % - 10 mass %, <1> It is the water dispersion type resin composition in any one of thru|or <5>.

<7> It is the water dispersion type resin composition in any one of <1>-<6> whose glass transition temperature of the said (meth)acrylic resin is 30 degreeC - 120 degreeC.

<8> The water-dispersible resin composition according to any one of <1> to <7>, further comprising a crosslinking agent.

It is an easily adhesive film which has a <9> base material and the easily adhesive layer formed using the water dispersion type resin composition in any one of <1>-<8>.

<10> Including a step of polymerizing a monomer constituting a (meth)acrylic resin in the presence of a polyester resin and an aqueous medium, including a structural unit derived from a vinyl-based monomer having an aryl group, the total mass of all structural units A method of producing a water-dispersible resin composition for producing a water-dispersible resin composition containing a (meth)acrylic resin and a polyester resin having a content rate of 60% by mass or more of a structural unit derived from a vinyl-based monomer having an aryl group.

According to the present invention, regardless of the material of the functional layer to be applied, the water-dispersible composition, the easily-adhesive film, and the water-dispersible resin composition are excellent in easy adhesion to both the functional layer and the base material and capable of suppressing the generation of iris-shaped reflected light. this is provided

Hereinafter, the water dispersion type resin composition of this invention is demonstrated in detail. In addition, in the present invention, "~" in the numerical range means that the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively.

In the numerical range described step by step in the present specification, the upper limit or lower limit described in a numerical range may be substituted with the upper limit or lower limit of the numerical range described in other steps. In addition, in the numerical range described in this specification, you may substitute the value shown in the Example for the upper limit or lower limit described in a certain numerical range.

In the present specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when a plurality of substances corresponding to each component are present in the composition.

A combination of preferred aspects herein is a more preferred aspect.

In the present specification, easy adhesion means that the water-dispersible resin composition of the present invention is easy to adhere to both the film and the functional layer as the base material, and peeling hardly occurs after adhesion.

As used herein, the (meth)acrylic resin refers to a polymer formed by polymerization of at least a monomer having a (meth)acryloyl group as a main component. The main component in (meth)acrylic resin means the thing with many content rate (mass %) among the monomer components which form a polymer. For example, in the case of (meth)acrylic resin, it means that the content rate of the structural unit derived from the (meth)acrylate monomer used as a main component is 50 mass % or more of all structural units.

In this specification, "(meth)acryl" means to include both "acryl" and "methacryl", and "(meth)acrylate" means to include both "acrylate" and "methacrylate" and "(meth)acryloyl" means including both "acryloyl" and "methacryloyl".

«Water Dispersion Resin Composition»

The water-dispersible resin composition of the present invention contains a (meth)acrylic resin and a polyester resin, and the (meth)acrylic resin includes a structural unit derived from a vinyl-based monomer having an aryl group, and the total mass of the total structural unit. It is obtained by polymerizing the monomer constituting the (meth)acrylic resin in the presence of the polyester resin and the aqueous medium, and the content of the structural unit derived from the vinyl monomer having an aryl group is 60% by mass or more. The water-dispersible resin composition of the present invention may further contain components other than those described above as needed.

The water dispersion type resin composition of the present invention has excellent easy adhesion to both the functional layer and the base material regardless of the material of the functional layer to be applied, and suppresses the occurrence of iris-shaped reflected light (hereinafter also referred to as "rainbow mark"). It is possible. Although this reason is not clear, it is guessed as follows.

In general, the compatibility between (meth)acrylic resin and polyester resin is poor, and a water-dispersible resin composition prepared by separately polymerizing (meth)acrylic resin and polyester resin and mixing these two resins (hereinafter referred to as “water-dispersion blend”) Also referred to as "resin composition"), the polyester resin tends to exist in the vicinity of the interface of the (meth)acrylic resin. For this reason, the polyester resin tends to come out on the surface layer of particle|grains, and it is easy to phase-separate. When an easily adhesive layer is formed using such a blended resin, it may not be possible to sufficiently obtain easy adhesion to the functional layer.

The water dispersion type resin composition of this invention contains the (meth)acrylic resin and polyester resin obtained by making a polyester resin into seed particle (henceforth "seed") and carrying out seed polymerization. In the seed polymerization, for example, a monomer for synthesizing a (meth)acrylic resin is added to a mixed solution in which a polyester resin is dispersed or dissolved in an aqueous medium, and a polymerization reaction using the polyester resin as a nucleus is performed. It is estimated that the resin particle obtained by seed polymerization takes the structure in which the (meth)acrylic resin and polyester resin entangled with each other inside the resin particle. For this reason, in the water dispersion type resin composition of the present invention, phase separation is difficult to occur, and easy adhesion tends to be improved even for functional layers of different materials, such as a hard coat film and a prism sheet.

Since the (meth)acrylic resin used in the water-dispersible resin composition of the present invention contains a structural unit derived from a vinyl-based monomer having an aryl group, a (meth)acrylic resin containing a structural unit derived from a vinyl-based monomer that does not have an aryl group It becomes possible to show a high refractive index compared with . In addition, the polyester resin used for the water dispersion type resin composition of the present invention exhibits a higher refractive index than the (meth)acrylic resin. The water dispersion type resin composition of the present invention contains such a (meth)acrylic resin and a polyester resin, and since the (meth)acrylic resin is obtained by seed polymerization with a polyester resin as a nucleus, it is difficult to cause phase separation and tends to exhibit a suitable refractive index. have.

When the functional layer is laminated on the easily adhesive layer formed of the water dispersion type resin composition of the present invention, the refractive index value of the easily adhesive layer formed of the water dispersion type resin composition of the present invention is close to the refractive index value of the functional layer. It is estimated that the iris-shaped reflected light is suppressed.

For this reason, it is estimated that this water dispersion type resin composition is excellent in easy adhesion to both the functional layer and the base material regardless of the material of the functional layer to be applied, and it is possible to suppress the generation of iris-shaped reflected light.

Hereinafter, the detail of each component used for the water dispersion type resin composition of this invention is demonstrated.

<(meth)acrylic resin>

The water dispersion type resin composition of this invention contains a (meth)acrylic resin. The (meth)acrylic resin in the present invention includes a structural unit derived from a vinyl monomer having an aryl group (hereinafter also referred to as an "aryl group-containing monomer"), The content rate of the structural unit derived from a system monomer is 60 mass % or more, It is obtained by superposing|polymerizing the monomer which comprises the said (meth)acrylic resin in presence of the polyester resin and aqueous medium mentioned later.

The water-dispersible resin composition of the present invention further comprises a (meth)acrylic resin different from the (meth)acrylic resin containing a structural unit derived from an aryl group-containing monomer, if necessary, in a range that does not impair the effects of the present invention, there may be

When the (meth)acrylic resin includes a structural unit derived from a vinyl-based monomer having an aryl group, the refractive index of the easily adhesive layer formed of the water-dispersible resin composition tends to be high. The vinyl monomer having an aryl group is not particularly limited as long as it has a vinyl group and is a polymerizable compound. Examples of the vinyl-based monomer having an aryl group include monomers in which an aryl group is introduced or substituted in a compound having a vinyl group, such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinylsulfonic acid, ethyleneimine, vinylpyridine, and vinylamine. have.

The aryl group-containing monomer is not particularly limited, and various (meth)acrylic acid aryl esters and styrene, such as benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate, are exemplified.

An aryl group containing monomer may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of the reactivity of the polymerization reaction, the aryl group-containing monomer preferably contains at least one selected from the group consisting of benzyl (meth)acrylate and phenoxyethyl (meth)acrylate, and includes benzyl (meth)acrylate. It is more preferable to

From the viewpoint of easy adhesion, the aryl group-containing monomer preferably contains at least one selected from the group consisting of benzyl methacrylate and phenoxyethyl methacrylate.

The content rate of the structural unit derived from an aryl group containing monomer with respect to the total mass of all structural units is 60 mass % or more. When the content of the structural unit derived from the aryl group-containing monomer is less than 60% by mass, it tends to be difficult to obtain a refractive index capable of suppressing a rainbow mark.

The content of the constituent units derived from the aryl group-containing monomer is preferably 70 mass % or more, more preferably 80 mass % or more, and still more preferably 90 mass % or more, with respect to the total mass of all constituent units from the viewpoint of increasing the refractive index. . Moreover, 100 mass % or less is preferable from an easily adhesive viewpoint, and, as for the content rate of the structural unit derived from an aryl group containing monomer, 98 mass % or less is more preferable.

The (meth)acrylic resin used in the water-dispersible resin composition of the present invention includes a structural unit derived from a monomer having a carboxy group (hereinafter also referred to as “carboxy group-containing monomer”) in addition to the structural unit derived from the aryl group-containing monomer; It is preferable to further include the structural unit derived from the monomer (henceforth "methylol group containing monomer") which has a methylol group.

That is, the (meth)acrylic resin used in the water-dispersible resin composition of the present invention is a monomer comprising a carboxyl group-containing monomer and a methylol group-containing monomer in addition to the aryl group-containing monomer in the presence of the polyester resin and aqueous medium detailed below. It is preferably obtained by polymerizing

When the (meth)acrylic resin contains a structural unit derived from a carboxyl group-containing monomer, a methylol group and a crosslinking agent described later react respectively to form a crosslinked structure. Thereby, irrespective of the material of the functional layer applied, the easy adhesion to both the functional layer and the base material tends to be more easily improved. In addition, when the (meth)acrylic resin contains a structural unit derived from a methylol group-containing monomer, a crosslinked structure tends to be formed by a condensation reaction between methylol groups (that is, a self-crosslinking reaction). It becomes easy to improve the easy adhesiveness with respect to it.

The carboxyl group-containing monomer is not particularly limited. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, 2-(meth)acryloyloxyethyl succinic acid, monohydroxyethyl maleate ( Meth)acrylate, monohydroxyethyl fumarate (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, 1,2-dicarboxycyclohexane monohydroxyethyl (meth)acrylate, (meth)acrylic acid dimer and ω-carboxy-polycaprolactone mono (meth)acrylate.

A carboxyl group containing monomer may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of reactivity with the crosslinking agent, the carboxyl group-containing monomer preferably contains at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and ω-carboxy-polycaprolactone mono (meth)acrylate, acrylic acid and It is more preferable that at least 1 sort(s) selected from the group which consists of methacrylic acid is included, and it is more preferable that methacrylic acid is included.

From the viewpoint of easy adhesion, the carboxyl group-containing monomer is particularly preferably containing at least one selected from the group consisting of methacrylic acid and ω-carboxy-polycaprolactone monomethacrylate.

From the viewpoint of good crosslinking reaction with respect to the methylol group and the crosslinking agent described later and improving the easy adhesion to both the functional layer and the base material regardless of the material of the functional layer to be applied, the content of the constituent units derived from the carboxyl group-containing monomer is the total 0.5 mass % - 15 mass % are preferable with respect to the gross mass of a structural unit, 1 mass % - 10 mass % are more preferable, 2 mass % - 8 mass % are still more preferable.

The methylol group-containing monomer is not particularly limited. Examples of the methylol group-containing monomer include N-methylolacrylamide, N-methylolmethacrylamide, dimethylolacrylamide, dimethylolmethacrylamide, N-butylolacrylamide, and N-butylolmethacrylamide. can be heard Among these, N-methylolacrylamide is preferable as a methylol group-containing monomer from a reactive viewpoint of a self-crosslinking reaction.

From the viewpoint of improving the self-crosslinking reaction between the methylol group-containing monomers and improving the easy adhesion to both the functional layer and the base material, the content of the structural units derived from the methylol group-containing monomers relative to the total mass of the total structural units is 0.5 Mass % - 10 mass % are preferable, 1.0 mass % - 8 mass % are more preferable, 1.5 mass % - 5 mass % are still more preferable.

As a ratio of the total of the structural unit derived from the aryl group-containing monomer, the structural unit derived from the carboxyl group-containing monomer, and the structural unit derived from the methylol group, 70 mass % or more with respect to the total mass of all structural units is preferable, 75 Mass % or more is more preferable, 80 mass % or more is still more preferable, and 90 mass % or more is especially preferable.

The (meth)acrylic resin used in the water-dispersible resin composition of the present invention is a structural unit derived from the aryl group-containing monomer, a structural unit derived from the carboxyl group-containing monomer, and a structural unit derived from the methylol group-containing monomer. You may further include the structural unit derived from (meth)acrylate.

When the (meth)acrylic resin includes a structural unit derived from an alkyl (meth)acrylate, the alkyl (meth)acrylate is preferably an unsubstituted alkyl (meth)acrylate, and the type thereof is not particularly limited. The alkyl group of the alkyl (meth)acrylate may be linear or branched. The range of 1-18 is preferable and, as for carbon number of the alkyl group of alkyl (meth)acrylate, the range of 1-12 is more preferable. If the number of carbon atoms of the alkyl group is within the above range, the easy adhesion to both the functional layer and the base material tends to be excellent regardless of the material of the functional layer applied.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth) acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate. Alkyl (meth)acrylate may be used individually by 1 type, and may use 2 or more types together.

The alkyl (meth)acrylate preferably contains at least one of methyl (meth)acrylate and ethyl (meth)acrylate from the viewpoint of easy adhesion.

Regardless of the material of the functional layer to be applied, the content of constituent units derived from alkyl (meth)acrylate relative to the total mass of all constituent units from the viewpoint of improving the refractive index while improving the easy adhesion to both the functional layer and the base material As such, 5 mass % - 30 mass % are preferable, and 10 mass % - 20 mass % are more preferable.

The (meth)acrylic resin used in the water-dispersible resin composition of the present invention contains a structural unit derived from an aryl group-containing monomer, a structural unit derived from a carboxyl group-containing monomer, and a methylol group-containing monomer within the range in which the effect of the present invention is exhibited. You may also include other structural units (henceforth "other structural unit") other than the structural unit derived from the structural unit derived from an alkyl (meth)acrylate. The monomer constituting the other structural unit is not particularly limited as long as it can be copolymerized with the aryl group-containing monomer, and may be appropriately selected according to the purpose.

Examples of the monomer constituting the other structural unit include a hydroxyl group, an alkylene oxide group, a glycidyl group, an amide group, an N-substituted amide group, an aryl group such as a tertiary amino group, a monomer having a functional group other than a carboxy group and a methylol group, and a polyfunctional group. and acrylic monomers.

As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acryl rate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and 3-methyl-3-hydroxybutyl (meth)acrylate can be heard

Examples of the monomer having an alkylene oxide group include methoxyethyl (meth) acrylate, 2-(ethoxyethoxy) ethyl acrylate, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, meth and oxy polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxy polyethylene glycol (meth) acrylate.

Examples of the monomer having a glycidyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, glycidyl ( and meta) allyl ether and 3,4-epoxycyclohexyl (meth) allyl ether.

Examples of the monomer having an amide group or an N-substituted amide group include acrylamide, methacrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N- Toxymethyl (meth)acrylamide, N-propoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-tert-butyl acrylamide, N-octyl acrylamide, diacetone acrylamide, etc. can be heard

Examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide.

Examples of the polyfunctional acrylic monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, capro Lactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, di(meth)acryloxyethyl isocyanurate, tricyclodecanedimethanol (meth)acrylate, dimethyloldicyclopentane Di(meth)acrylate, ethylene oxide modified hexahydrophthalic acid di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, neopentyl glycol modified trimethylpropane di(meth)acrylate, trimethylolpropane tri(meth) ) acrylate, dipentaerythritol tri(meth)acrylate, diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

As a weight average molecular weight (Mw) of the (meth)acrylic resin used for the water dispersion type resin composition of this invention, 500,000-5,000,000 are preferable, 500,000-3,000,000 are more preferable, 1,000,000-3,000,000 are still more preferable.

The weight average molecular weight (Mw) of (meth)acrylic resin is the value measured by the following method.

(Method for measuring weight average molecular weight (Mw))

It measures according to the following (1)-(3).

(1) A (meth)acrylic resin solution is applied to a release paper and dried at room temperature all day to obtain a film-like (meth)acrylic resin.

(2) The film-like (meth)acrylic resin obtained in the above (1) is dissolved in dimethylformamide containing 1 mM lithium bromide so as to have a solid content of 0.5% by mass. Thereafter, the solution is filtered through a membrane filter (HPLC Millex-LH, pore diameter 0.45 μm, diameter 25 mm).

(3) The weight average molecular weight (Mw) of (meth)acrylic resin is measured as a standard polystyrene conversion value using gel permeation chromatography (GPC) on the following conditions.

(Condition)

GPC: GL7420 GPC (product of GL Science Co., Ltd.)

Column: Using SHODEX SB-806M HQ (manufactured by Showa Denko Co., Ltd.)

Mobile phase solvent: dimethylformamide with 1 mM lithium bromide

Flow rate: 0.5ml/min

Column temperature: 40°C

Since the particles of the resin dispersed in water do not become too large, the glass transition temperature (Tg) of the (meth)acrylic resin is -10°C to 120°C from the viewpoint of improving adhesion to the base material during heat treatment in the film stretching step. C is preferable, 30 degreeC - 120 degreeC are more preferable, and 50 degreeC - 80 degreeC are still more preferable.

The Tg of the (meth)acrylic resin is a value obtained by converting the absolute temperature (K) obtained by the calculation from the following formula (1) into the Celsius temperature (°C).

1/Tg=m1/Tg1+m2/Tg2+… +m(k-1)/Tg(k-1)+mk/Tgk … (Equation 1)

In formula 1, Tg1, Tg2, ... , Tg(k-1), and Tgk are glass transition temperatures expressed in absolute temperature (K) when each monomer constituting the (meth)acrylic resin is used as a homopolymer. m1, m2, … , m(k-1), mk represents the mole fraction of each monomer constituting the (meth)acrylic resin, respectively, and m1+m2+... +m(k-1)+mk=1.

In addition, "the glass transition temperature expressed by the absolute temperature (K) when the homopolymer is used" refers to the glass transition temperature expressed by the absolute temperature (K) of the homopolymer prepared by polymerization of the monomer alone. The glass transition temperature of the homopolymer is measured using a differential scanning calorimetry (DSC) (Seiko Instruments product, EXSTAR6000) for the homopolymer under the conditions of 10 mg of measurement sample and a temperature increase rate of 10 ° C. / min in a nitrogen stream. The inflection point of the DSC curve was taken as the glass transition temperature of the homopolymer.

The “glass transition temperature expressed in degrees Celsius (° C.) of the homopolymer” of representative monomers is 5° C. for methyl acrylate, 103° C. for methyl methacrylate, -27° C. for ethyl acrylate, and n-butyl acrylate is -57°C, 2-ethylhexylacrylate is -76°C, 2-hydroxyethylacrylate is -15°C, 4-hydroxybutylacrylate is -39°C, and t-butylacrylate is 41 ° C, acrylic acid 163 ° C, methacrylic acid 185 ° C, N-methylolacrylamide 110 ° C, benzyl acrylate 6 ° C, benzyl methacrylate 54 ° C, phenoxyethyl acrylate is -22 °C, and phenoxyethyl methacrylate is 54 °C. For example, the glass transition temperature (Tg) of a (meth)acrylic resin can be suitably adjusted by using the monomer from which the glass transition temperature of a homopolymer differs.

Also, by subtracting 273 from the absolute temperature (K), the absolute temperature (K) can be converted to the Celsius temperature (℃), and by adding 273 to the Celsius temperature (℃), the Celsius temperature (℃) is converted to the absolute temperature (K). can be converted

Regardless of the material of the applied functional layer, the content of (meth)acrylic resin in the water dispersion type resin composition in terms of easy adhesion and refractive index to both the functional layer and the base material is 20 with respect to the total mass of the solid content of the water dispersion type resin composition. Mass % - 95 mass % are preferable, and 25 mass % - 90 mass % are more preferable.

In addition, "solid content" is the residual amount which removed the aqueous medium from the water dispersion type resin composition.

<Polyester resin>

The water dispersion type resin composition of the present invention contains a polyester resin. When the water dispersion type resin composition contains the polyester resin, it becomes possible to further increase the refractive index. In addition, since the water dispersion type resin composition contains a (meth)acrylic resin obtained by seed polymerization of a monomer constituting a (meth)acrylic resin using a polyester resin as a seed, the (meth)acrylic resin and the polyester resin are entangled with each other. is presumed to have For this reason, in the water-dispersible resin composition of the present invention including (meth)acrylic resin and polyester resin, phase separation is difficult to occur, and the easy adhesion to both the functional layer and the base material is improved regardless of the material of the applied functional layer. it becomes possible to do

As a polyester resin used for the water dispersion type resin composition of this invention, the polycondensate of polyhydric carboxylic acid and polyhydric alcohol is mentioned, for example. Moreover, a commercial item may be used and the polyester resin may use what was synthesize|combined.

As polyhydric carboxylic acid, for example, aliphatic dicarboxylic acid (oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenylsuccinic acid, adipic acid, sebacic acid, etc.), alicyclic dicarboxylic acid main acids (cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, etc.) and their anhydrides or lower (for example, 1 to 5 carbon atoms) alkyl esters have. Among these, as polyhydric carboxylic acid, aromatic dicarboxylic acid is preferable.

Polyhydric carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.) and dihydric alcohols such as aromatic diols (such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A); and trihydric or higher alcohols such as glycerin, trimethylolpropane, and pentaerythritol.

Among these, as a polyhydric alcohol, an aliphatic diol is preferable. A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

As the polyester resin used in the water-dispersible resin composition of the present invention, a polyester resin obtained by condensation polymerization of an aromatic dicarboxylic acid and an aliphatic diol is preferable, and a polyester resin having a naphthalene skeleton is more preferable. Examples of such polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). have.

Among these, polybutylene naphthalate (PBN) or polyethylene naphthalate (PEN) is preferable from a viewpoint of improving refractive index and easy adhesiveness, and polyethylene naphthalate (PEN) is more preferable.

As the polyester resin used in the water-dispersible resin composition of the present invention, a water-soluble polyester resin or a water-dispersible polyester resin is preferable. When the monomer constituting the (meth)acrylic resin is seed-polymerized using a water-soluble or water-dispersible polyester resin, the (meth)acrylic resin is formed by polymerization of the monomer using the polyester resin as the seed as the nucleus. It is possible to have a structure in which the resin and the (meth)acrylic resin are entangled with each other, the refractive index is improved, and the easy adhesion to both the functional layer and the base material is improved regardless of the material of the applied functional layer.

In the present specification, the water-soluble polyester resin means that the polyester resin is dissolved in water at 23° C. by 1 mass % or more. In addition, as used herein, the water-dispersible polyester resin is a polyester resin having a hydrophobic portion and a hydrophilic portion in a molecule. When the polyester resin is dispersed in an aqueous medium, resin particles are formed in the aqueous medium, and the resin particles are dispersed in the aqueous medium. It means the polyester resin which shows the state which has become.

As water-soluble polyester resins or water-dispersible polyester resins, plastics Z-687, Z-690, Z-221, Z-446, Z-561, Z-450, Z-565, Z-850, Z-3308, RZ -105, RZ-570, Z-730, RZ-142 (above, manufactured by Koo Chemical Industry Co., Ltd.), Fesresin TWX-797 (above, manufactured by Takamatsu Oil Co., Ltd.), Hydran HW350 (above, DIC) Those sold under product names such as Co., Ltd. products are mentioned.

From the viewpoint of improving the refractive index and easy adhesion, the content of the polyester resin in the water-dispersible resin composition is preferably 5% by mass to 80% by mass, and 10% by mass to 70% by mass relative to the total mass of the solid content of the water-dispersible resin composition. % is more preferable.

As a content ratio of the (meth)acrylic resin with respect to the polyester resin in a water dispersion type resin composition, 30/70-90/10 are preferable on a mass basis. It becomes possible to raise refractive index more that the content rate of the (meth)acrylic resin with respect to a polyester resin is 30/70 or more. In addition, when the content ratio of the (meth)acrylic resin to the polyester resin is 90/10 or less, the easy adhesion to both the functional layer and the base material tends to be improved regardless of the material of the functional layer applied. As a content ratio of the (meth)acrylic resin with respect to a polyester resin from a viewpoint of making a refractive index and easy adhesiveness compatible, 50/50-80/20 are more preferable, and 50/50-70/30 are still more preferable.

Regardless of the material of the applied functional layer, the ratio of the polyester resin used in the seed polymerization from the viewpoint of improving the easy adhesion to both the functional layer and the base material is based on the total mass of the polyester resin contained in the water dispersion type resin composition. 60 mass % or more is preferable, 80 mass % or more is more preferable, and 90 mass % or more is still more preferable.

As a weight average molecular weight (Mw) of a polyester resin, 5,000-100,000 are preferable. As a weight average molecular weight (Mw) of a polyester resin from a viewpoint of manufacturing stable particle|grains, 5,000-80,000 are preferable and 5,000-50,000 are more preferable. In addition, a weight average molecular weight (Mw) can be measured with the following method.

The weight average molecular weight (Mw) of the polyester resin is a value measured by the following method, respectively.

(Method for measuring weight average molecular weight (Mw))

It measures according to the following (1)-(3).

(1) A polyester resin is applied to a release paper and dried at 100°C for 2 minutes to obtain a film-like polyester resin.

(2) The film-like polyester resin obtained in the above (1) is dissolved with tetrahydrofuran so as to have a solid content of 0.2% by mass.

(3) The weight average molecular weight (Mw) of the polyester resin is measured as a standard polystyrene conversion value using gel permeation chromatography (GPC) under the following conditions.

(Condition)

GPC: HLC-8220 GPC [manufactured by Tosoh Corporation]

Column: Using 4 TSK-GEL GMHXL

Mobile phase solvent: tetrahydrofuran

Flow rate: 0.6ml/min

Column temperature: 40°C

<Aqueous medium>

The water-dispersible resin composition of the present invention contains an aqueous medium. It does not restrict|limit especially as an aqueous medium, According to the objective, it can select suitably. As an aqueous medium, water, the liquid mixture of water, and an alcohol solvent, etc. are mentioned. From the viewpoint of stability of the water-soluble polyester resin or the water-dispersible polyester resin, water is preferable as the aqueous medium.

Examples of the alcohol-based solvent include methyl alcohol, ethyl alcohol and propyl alcohol.

The content rate in particular of the aqueous medium in the water dispersion type resin composition is not restrict|limited, With respect to the total mass of the water dispersion type resin composition, 60 mass % - 95 mass % is preferable, 65 mass % - 90 mass % is more preferable, 70 mass % -85 mass % is more preferable.

<Surfactant>

The water-dispersible resin composition of the present invention may contain a surfactant. There is no restriction|limiting in particular as surfactant used for the water dispersion type resin composition, A well-known thing can be used. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, as surfactant from a stability viewpoint of a resin particle, an anionic surfactant and a nonionic surfactant are preferable, and an anionic surfactant is more preferable.

Surfactant may be used individually by 1 type, and may use 2 or more types together.

Examples of the anionic surfactant include alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, alkyl sulfates such as sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl ether sulfates such as polyoxyethylene polycyclic phenyl ether. and fatty acid salts such as sodium stearate soap, and cellulose derivatives such as carboxymethyl cellulose. From the viewpoint of polymerizability, the anionic surfactant is preferably an alkylsulfonate.

Examples of the anionic surfactant include those marketed under product names such as "Neopelex G-15", "Neopelex G-25", and "Neopelex G-65" (above, manufactured by Kao Co., Ltd.) can

Examples of the nonionic surfactant include polyoxyethylene polycyclic phenyl ether such as polyoxyethylene biphenyl ether, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyalkylene derivative such as polyoxyalkylene alkyl ether, sorbitan sorbitan fatty acid esters such as monolaurate, glycerin fatty acid esters such as glycerol monostearate, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, and cellulose derivatives such as methylcellulose, ethylcellulose, and hydroxypropylcellulose can

As a nonionic surfactant from an emulsion-polymerizable viewpoint, polyoxyethylene alkyl ether is preferable.

As a nonionic surfactant, "Emulgen A-60", "Emulgen A-90", "Emulgen B-66" (above, Kao Co., Ltd. product), "Neugen EA-197D", "Neugen EA" -207D" (above, Daiichi Kogyo Pharmaceutical Co., Ltd. product) and the like are those marketed by product names.

As for content of surfactant, 0 mass parts - 15 mass parts are preferable with respect to a total of 100 mass parts of (meth)acrylic resin and polyester resin from a dispersibility viewpoint to the aqueous medium of (meth)acrylic resin, 0.5 mass part - 10 mass parts A mass part is more preferable.

<Crosslinking agent>

It is preferable that the water dispersion type resin composition of this invention contains a crosslinking agent. The crosslinking agent reacts with a crosslinkable functional group such as a carboxyl group, a methylol group and a hydroxyl group. The crosslinking agent is not particularly limited, and known ones such as an epoxy-based crosslinking agent, an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, an oxazoline-based crosslinking agent, and a metal chelate-based crosslinking agent can be used. Among these, as the crosslinking agent, a melamine-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent are preferable, and a melamine-based crosslinking agent and an oxazoline-based crosslinking agent are more preferable from the viewpoint of reactivity with the crosslinking functional group and the physical properties of the coating film after the crosslinking reaction. , more preferably a melamine-based crosslinking agent. These crosslinking agents may be used individually by 1 type, and may use 2 or more types together.

Examples of the melamine-based crosslinking agent include a methylolated melamine resin obtained by condensing melamine or a melamine derivative and formaldehyde, an etherified melamine resin obtained by reacting methylolated melamine with a lower alcohol to etherify partially or completely, and mixtures thereof. Among these, a methylolation melamine resin is preferable as a melamine-type crosslinking agent from a viewpoint of the reactivity with the said crosslinkable functional group and the physical property of the coating film after a crosslinking reaction.

As a melamine-based crosslinking agent, by product names such as "Nika Rack MW-12LF", "Nika Rack MW-22", "Nika Rack MW-30", and "Nika Rack MX-035" (above, manufactured by Sanwa Chemical) commercially available ones are mentioned.

The carbodiimide-based crosslinking agent includes a carbodiimide compound and is not particularly limited as long as it is a compound having one or more carbodiimide groups in the molecule. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide, N,N'-di(o-toluyl)carbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'- monofunctional carbodiimide compounds such as bis(2,6-diisopropylphenyl)carbodiimide; p-phenylene-bis(2,6-xylylcarbodiimide), p-phenylene-bis(t-butylcarbodiimide), p-phenylene-bis(mesitylcarbodiimide), tetramethylene- bifunctional carbodiimide compounds such as bis(t-butylcarbodiimide) and cyclohexane-1,4-bis(methylene-t-butylcarbodiimide); Polyfunctional carbodiimide compounds, such as a condensate of an isocyanate monomer, etc. are mentioned.

Among these, a polyfunctional carbodiimide compound is preferable. Here, the polyfunctional carbodiimide compound refers to a compound having two or more carbodiimide groups. As said polyfunctional carbodiimide compound, "Carbodilite (registered trademark) V-02-L2", "Carbodilite (registered trademark) SV-02", "Carbodilite (registered trademark) V-10" (Nit What is marketed by product names, such as Shinbo Chemical Co., Ltd. product) is mentioned.

As an oxazoline crosslinking agent, "Epocross (registered trademark) WS-700", "Epocross (registered trademark) WS-500", "Epocross (registered trademark) WS-300", "Epocross (registered trademark) K-2010E" , ", "Epocross (registered trademark) K-2020E", "Epocross (registered trademark) K-2030E" (product of Nippon Catalyst Co., Ltd.), etc., commercially available ones are mentioned.

The content of the crosslinking agent in the water-dispersible resin composition of the present invention is that of the (meth)acrylic resin and the polyester resin from the viewpoint of easy formation of a crosslinked structure with the crosslinkable functional group and good crosslinking reaction between the crosslinkable functional group and the crosslinking agent. The range of 5 mass parts - 40 mass parts is preferable with respect to a total of 100 mass parts, The range of 5 mass parts - 30 mass parts is more preferable, The range of 15 mass parts - 25 mass parts is still more preferable.

<Other ingredients>

The water-dispersible resin composition in the present invention may contain other components other than those described above as needed. Various additives, such as antioxidant, antistatic agent, a pH adjuster, an antifoamer, a ultraviolet absorber, a light stabilizer, and a water dispersion type filler, are mentioned as another component.

Examples of the water-dispersible filler include a titanium-based filler, a silica-based filler, and a zirconium-based filler. When the water-dispersible resin composition contains a water-dispersible filler, the refractive index tends to increase.

(Method for producing water-dispersible resin composition)

The method for producing a water-dispersible resin composition of the present invention includes a step of polymerizing a monomer constituting a (meth)acrylic resin in the presence of a polyester resin and an aqueous medium, and includes a structural unit derived from a vinyl-based monomer having an aryl group. and a water dispersion type resin composition containing a (meth)acrylic resin and a polyester resin in which the content of the structural unit derived from the vinyl-based monomer having the aryl group with respect to the total mass of the total structural unit is 60% by mass or more It is a manufacturing method of a resin composition.

The water dispersion type resin composition of this invention is manufactured by the following method, for example.

The water-dispersible resin composition of the present invention is a monomer mixture by mixing a step of dispersing or dissolving a polyester resin in an aqueous medium (hereinafter also referred to as a “polyester resin preparation step”), and a monomer component constituting the (meth)acrylic resin. Manufacturing having a step of obtaining (hereinafter also referred to as “pre-emulsion step”) and a step of polymerizing a monomer mixture in the presence of a polyester resin and an aqueous medium (hereinafter also referred to as “seed polymerization step”) can be obtained according to the method.

Moreover, a monomer mixture contains the aryl group containing monomer in the quantity from which the content rate with respect to the total mass of all the structural units of a (meth)acrylic resin becomes 60 mass % or more at least.

Hereinafter, the process in the manufacturing method of this embodiment is demonstrated in detail.

In addition, about the specific example and preferable aspect of the component used in each process, since it is as having described in each item of a water dispersion type resin composition, description is abbreviate|omitted here.

(Polyester resin preparation process)

The polyester resin preparation step includes a step of preparing an aqueous dispersion of the polyester resin by mixing and stirring while adding an aqueous medium to the polyester resin contained in the water dispersion type resin composition of the present invention. There is no restriction|limiting in particular about the method of mixing and stirring, A generally used mixing and stirring apparatus and, if necessary, a disperser such as an ultrasonic disperser or a high-pressure homogenizer can be used.

(Pre-emulsion process)

The pre-emulsion step includes a step of emulsifying and dispersing at least a monomer mixture including a constituent unit derived from an aryl group-containing monomer in the presence of a surfactant, and obtaining a pre-emulsion in which particles of the monomer constituting the (meth)acrylic resin are emulsified and dispersed. do.

(Seed polymerization process)

The seed polymerization step includes a step of polymerizing the obtained pre-emulsion in the presence of an aqueous dispersion of a polyester resin, and forming resin particles including a (meth)acrylic resin and a polyester resin.

That is, the resin particles after polymerization have a structure in which a (meth)acrylic resin and a polyester resin are entangled with each other.

The polymerization method in the seed polymerization step (hereinafter also referred to as "seed polymerization method") is not particularly limited, and a known method can be used. As the seed polymerization method, for example, a polyester resin serving as a seed and an aqueous medium such as water are put into a reaction vessel equipped with a thermometer, a stirring bar, a reflux condenser, a dropping funnel, etc. under a nitrogen stream, and the inside of the reaction vessel is heated. Next, a pre-emulsion is obtained by emulsifying in advance with an aqueous medium such as a monomer component, a surfactant, and water, and a monomer component other than the polyester resin serving as a seed. The method of advancing the reaction is mentioned.

40 degreeC - 100 degreeC are preferable, and, as for the polymerization temperature in a seed polymerization process, 50 degreeC - 100 degreeC are more preferable, for example.

1 hour - 8 hours are preferable, and, as for the polymerization time in a seed polymerization process, 2 hours - 6 hours are more preferable, for example.

The stirring time after adding the polymerization initiator as a solution of the aqueous medium is preferably 1 hour to 8 hours at 40° C. to 100° C., more preferably 2 hours to 6 hours at 50° C. to 100° C. from the viewpoint of reducing the residual monomer. do.

The addition of the polymerization initiator is preferably divided into two or more times, and the temperature and polymerization time for the last addition are preferably 40°C to 100°C, 1 hour to 8 hours, and 50°C to 100°C, 1 hour. ~8 hours is more preferable.

In the seed polymerization process, you may use various additives, such as a polymerization initiator, a reducing agent, a chain transfer agent, and a pH adjuster.

(Polymerization Initiator)

The polymerization initiator is not particularly limited as long as it can be used in a normal polymerization method, and a known polymerization initiator can be used. Examples of the polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, and hydrogen peroxide.

When using a polymerization initiator at a seed polymerization process, a polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

A polymerization initiator is used in the amount normally used. As usage-amount of a polymerization initiator, 0.1 mass part - 2 mass parts are preferable with respect to 100 mass parts of total amounts of the monomer which is a raw material, and 0.3 mass part - 1.5 mass parts are more preferable.

(reducing agent)

In the seed polymerization step, a reducing agent may be used together with the polymerization initiator.

Examples of the reducing agent include sodium metabisulfite, sodium sulfite, sodium hydrogen sulfite, sodium pyrosulfite, sodium pyrophosphate, thioglycolic acid, sodium thiosulfate, ascorbic acid, tartaric acid, citric acid, glucose and the like.

When using a reducing agent in a seed polymerization process, a reducing agent may be used individually by 1 type, and may use 2 or more types together.

The reducing agent is used in an amount normally employed. As usage-amount of a reducing agent, 0.1 mass part - 2 mass parts are preferable with respect to 100 mass parts of total amounts of the monomer which is a raw material, and 0.3 mass part - 1.5 mass parts are more preferable.

(different process)

The manufacturing method of this embodiment may have other processes other than a polyester resin preparation process, a pre-emulsion process, and a seed polymerization process as needed.

The average primary particle diameter of the resin particles contained in the water dispersion type resin composition is preferably 100 nm or less, more preferably 90 nm or less, and still more preferably 85 nm or less from the viewpoint of obtaining a uniform film thickness when the easily adhesive layer is formed. If the average primary particle diameter of the resin particles is 100 nm or less, the resin particles do not become too large, and when an easily adhesive layer is formed, a uniform film thickness is easily obtained, and the easily adhesive property tends to be excellent.

Moreover, there is no limitation in particular as for the lower limit of the average primary particle diameter of a resin particle, From a manufacturing efficiency improvement viewpoint, 10 nm or more is preferable, and 20 nm or more is more preferable.

In this specification, "average primary particle diameter of resin particles contained in water-dispersible resin composition" refers to pages 725 to 741 of "New Experimental Chemistry Lecture 4 Basic Technology 3 Light (II)", edition of the Japanese Chemical Society (Showa 51). It is a value measured by the dynamic light scattering method described in Maruzen Co., Ltd. issue on July 20. The specific method is as follows.

After diluting the water dispersion type resin composition with distilled water and sufficiently stirring and mixing, 5 ml of the water dispersion type resin composition is collected in a 10 mm glass cell using a Pasteur pipette and set in a dynamic light scattering photometer "Zetasizer 1000HS" (Malvern Co., Ltd.) . After preparing the diluted solution concentration of the aqueous dispersion of (meth)acrylic resin so that the count rate of the attenuation rate is 150Cps to 200Cps, the measurement result is computerized under the conditions of a measurement temperature of 25°C±1°C and a light scattering angle of 90°. The average primary particle diameter of the resin particle contained in a composition is calculated|required.

As a use of the water dispersion type resin composition of this invention, it can utilize suitably as an easily adhesive layer interposed between a base material and a functional layer in the optical film in liquid crystal display devices etc., for example.

Examples of the base material include sheets and films made of polyester-based resins, acetate-based resins, polyethersulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyolefin-based resins, and acrylic-based resins. can

As a functional layer, a hard-coat layer, a prism layer, a light-diffusion layer, etc. are mentioned, for example.

<Easy Adhesive Film>

The easily adhesive film of the present invention has a base material and an easily adhesive layer formed using the water-dispersible resin composition of the present invention. The easily adhesive layer is excellent in easy adhesion to functional layers such as a hard coat layer and a prism layer, and is excellent in suppression of occurrence of rainbow marks.

The easily adhesive film of the present invention can be produced by, for example, forming an easily adhesive layer by applying the water dispersion type resin composition of the present invention to a base material and drying it to cause a crosslinking reaction. The crosslinking agent may be included in the water dispersion type resin composition in advance, or may be mixed with the water dispersion type resin composition before application.

The method of forming the easily adhesive layer formed on the base material is not particularly limited, and known methods using a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, etc. are mentioned. have.

In the easily adhesive film of the present invention, the thickness of the easily adhesive layer formed on the base material is not particularly limited, and can be appropriately set according to the use or required performance. The thickness of the easily adhesive layer is preferably in the range of 50 nm to 300 nm.

In the easily adhesive film of the present invention, it is preferable that the transparency of the easily adhesive layer is high. Specifically, for example, the total light transmittance in the visible wavelength region (JIS K 7361 (1997)) is preferably 85% or more, and more preferably 90% or more. The haze of the easily adhesive layer (JIS K 7136 (2000)) is preferably less than 4.0%, more preferably less than 3.7%.

The base material constituting the easily adhesive film of the present invention may be selected from any material as long as the formation of an easily adhesive layer thereon is possible.

Examples of the material of the base material include polyester-based resins, acetate-based resins, polyethersulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyolefin-based resins, and acrylic resins.

Especially, as a base material, the base material of a polyester resin is preferable, and the base material of a polyethylene terephthalate (PET) resin is more preferable from a practical point.

The shape of the base material may be, for example, a film shape or a sheet shape.

Although the thickness of a base material can be selected according to a use, it is generally 500 micrometers or less. Among these, as a preferable thickness, it is the range of 5 micrometers - 300 micrometers, and about 10 micrometers - 200 micrometers can be illustrated as a more preferable range.

The refractive index of the easily adhesive layer constituting the easily adhesive film of the present invention is preferably 1.560 to 1.630, more preferably 1.565 to 1.624, and still more preferably 1.570 to 1.620 from the viewpoint of reducing iris-shaped reflected light.

In addition, in this specification, the refractive index is the value measured using the Abbe refractometer.

The easily adhesive film of this invention can be used suitably for bonding, such as an optical film of a liquid crystal display device. That is, the easily adhesive film of the present invention is, for example, a polarizing plate, a retardation plate, an antireflection film, a viewing angle magnifying film, and bonding of optical films such as a brightness increasing film, and the optical film and liquid crystal cell, glass substrate, protective film, etc. It can use suitably for bonding.

As a use of such an easily adhesive film, the use which provides functional layers, such as a hard-coat layer, a prism layer, and a light-diffusion layer, on an easily adhesive layer, and sets it as an optical film is mentioned.

These optical films are used as a member which comprises, for example, display devices, such as a liquid crystal display device and organic electroluminescent display, and input devices, such as a touch panel.

As a use of the easily adhesive film of this invention, since it is excellent in easy adhesiveness, the use which prepares either a hard-coat layer or a prism layer as a functional layer and uses it as an optical film is preferable. That is, it is preferable to use it as an easily adhesive film for hard-coat films or for prism sheets.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

[Production of aqueous dispersion containing (meth)acrylic resin]

(Production Example 1)

235.0 parts by mass of deionized exchanged water, water-dispersible polyester resin (Resin 1 for seed) (Koh Chemical Industry Co., Ltd. product, prascot Z-687) 171.4 mass parts was put, and it heated up at 78 degreeC, replacing the inside of reaction container with nitrogen.

Meanwhile, in another reaction vessel, 50.0 parts by mass of deionized water, 1.6 parts by mass of a surfactant (Neopelex G-65, manufactured by Kao Co., Ltd.) and 3.0 parts by mass of N-methylolacrylamide (NMAM) were added and stirred. , the pre-emulsion was prepared by adding and stirring a solution in which 92.0 parts by mass of benzyl methacrylate (BzMA) and 5.0 parts by mass of methacrylic acid (MAA) were mixed and stirred.

Next, while maintaining the internal temperature of the reaction vessel at 78°C, 2% by mass (3.0 parts by mass) of the preemulsion prepared above is added into the reaction vessel containing the resin 1 for the seed, and then 1.8% by mass of a 10% by mass aqueous solution of ammonium persulfate Parts and 0.9 mass parts of 10 mass % sodium metabisulfite aqueous solution were added, and the polymerization reaction was started. After the internal temperature of the reaction vessel reached 80°C, the remaining total amount of the preemulsion prepared above, 9.0 parts by mass of a 2% by mass ammonium persulfate aqueous solution, and 4.5 parts by mass of a 2% by mass aqueous sodium metabisulfite solution were uniformly ordered over 4 hours. was added and polymerized. After aging the obtained polymer at 80°C for 2 hours and cooling to room temperature, pH was adjusted with an appropriate amount of aqueous ammonia solution to obtain an aqueous dispersion containing a (meth)acrylic resin having a pH of 8.5. Solid content of the aqueous dispersion containing the obtained (meth)acrylic resin was 25 mass %.

In addition, "solid content" is the residual amount which removed the aqueous medium from the aqueous dispersion containing (meth)acrylic resin.

In addition, this polymerization method is seed polymerization which made seed particle|grains 1 which is a water-dispersible polyester resin for seeds.

<Measurement of average primary particle diameter of resin particles>

After diluting the aqueous dispersion containing the (meth)acrylic resin obtained above with distilled water, sufficiently stirring and mixing, using a Pasteur pipette in a glass cell of 10 mm in width and length to collect 5 ml of this, a dynamic light scattering photometer “Zetasizer 1000HS” (Malvern Co., Ltd. product). After preparing the diluted solution concentration of the aqueous dispersion containing the (meth)acrylic resin so that the count rate of the attenuation rate is 150Cps to 200Cps, the measurement result is computer-processed under the conditions of a measurement temperature of 25°C±1°C and a light scattering angle of 90° (meta ) The average primary particle diameter of the resin particles in the aqueous dispersion containing the acrylic resin was calculated. The average primary particle diameter of the resin particles was 55 nm.

(Preparation Example 2 to Preparation 19 and Preparation 22)

In Production Example 1, an aqueous dispersion containing a (meth)acrylic resin was prepared in the same manner as in Production Example 1 except that the monomers were changed as shown in Table 1 and the amount of the initiator was appropriately prepared. Table 1 shows the solid content composition (mass %) of the obtained aqueous dispersion containing the (meth)acrylic resin and Tg of the (meth)acrylic resin. Tg is measured and calculated by the method previously described.

Moreover, this polymerization method is seed polymerization which used the water-dispersible polyester resin as seed particle.

(Production Example 20)

In a reaction vessel equipped with a thermometer, a stirring bar, a reflux condenser and a dropping funnel, 140.0 parts by mass of deionized water and 1.6 parts by mass of a surfactant (Kao Co., Ltd., Neopelex G-65) were placed, and the inside of the reaction vessel was purged with nitrogen. The temperature was raised to 58 ° C.

On the other hand, in another reaction vessel, 40.0 parts by mass of deionized water and 1.6 parts by mass of a surfactant (Kao Co., Ltd., Neopelex G-65) and a surfactant (Daichi Kogyo Pharmaceutical Co., Ltd., Neugen EA-) 197D) 15.4 parts by mass and 3.0 parts by mass of N-methylolacrylamide (NMAM) were added and stirred, and then a solution of 92.0 parts by mass of benzyl methacrylate (BzMA) and 5.0 parts by mass of methacrylic acid (MAA) was mixed, A pre-emulsion was prepared by stirring.

Next, after adding 2 mass % (3.14 mass parts) of the preemulsion prepared above in the reaction vessel while maintaining the internal temperature of the reaction vessel at 58 ° C., 2.0 mass parts of 10 mass % ammonium persulfate aqueous solution and 10 mass % meta 1.8 mass parts of sodium bisulfite aqueous solution was added, and emulsion polymerization reaction was started. After the internal temperature of the reaction vessel reached 60° C., the remaining total amount of the preemulsion prepared above, 10.0 parts by mass of a 2% by mass aqueous solution of ammonium persulfate and 9.0 parts by mass of a 2% by mass aqueous solution of sodium metabisulfite were uniformly distributed over 4 hours. They were added sequentially and emulsion polymerization was carried out. After aging the obtained emulsion polymer at 60 degreeC for 2 hours, after cooling to room temperature, pH adjustment was performed with the appropriate amount of aqueous ammonia solution, and the (meth)acrylic resin aqueous dispersion of pH 8.5 was obtained. Solid content of the aqueous dispersion containing the obtained (meth)acrylic resin was 35.1 mass %. In addition, when the average primary particle diameter of the resin particle in the aqueous dispersion containing the (meth)acrylic resin was measured by the method mentioned above, the average primary particle diameter of the resin particle was 51 nm.

In addition, this polymerization method is emulsion polymerization.

(Preparation Example 21)

In a stainless container, 110 parts by mass of methyl methacrylate (MMA), 130 parts by mass of ethyl acrylate (EA), 60.0 parts by mass of methacrylic acid (MAA), and 3.0 parts by mass of n-dodecyl mercaptan were put and mixed with stirring.

60 parts by mass and 200 parts by mass of isopropyl alcohol, 2-2'-azobis-2,4-dimethylvaleronitrile (AIBN) 0.6 in the above mixed solution in a reaction vessel equipped with a stirrer, a reflux cooling tube, a thermometer and a dropping funnel It heated up until refluxed by adding a mass part.

After holding|maintaining for 20 minutes in a reflux state, the liquid mixture of 50.0 mass parts of isopropyl alcohol, and AIBN 1.7 mass parts was dripped for 120 minutes after hold|maintaining for 20 minutes. 20 minutes after the completion of the dropping, a mixture of 40.0 parts by mass of isopropyl alcohol and 1.7 parts by mass of AIBN was added dropwise for 120 minutes, and reflux was maintained for 120 minutes after the completion of the dropping.

After cooling the reaction solution to 50 ° C. or less, it was transferred to a reaction vessel equipped with a stirrer and a decompression facility, and 60.0 parts by mass of 25 mass % aqueous ammonia and 900 parts by mass of deionized water were added, and isopropyl alcohol and unreacted monomers were recovered under reduced pressure at 60 ° C. Resin 2 for seeds which is a water-dispersible (meth)acrylic resin was obtained.

Resin 2 for seeds which is the obtained water-dispersible (meth)acrylic resin was 23.5 mass % of nonvolatile matter, pH 6.9, and the viscosity was 40 mPa*s. Moreover, after drying the obtained aqueous dispersion of (meth)acrylic resin and dissolving in tetrahydrofuran (THF), as a result of performing GPC measurement on the conditions previously mentioned, the weight average molecular weight (Mw) (polystyrene conversion) was 15,000.

In a reaction vessel equipped with a thermometer, a stirring bar, a reflux condenser, and a dropping funnel, 268.0 parts by mass of deionized water and 182.4 parts by mass of Resin 2 for seed, which is a water-dispersible (meth)acrylic resin, were placed, and the inside of the reaction vessel was purged with nitrogen at 80 ° C. was heated to

Meanwhile, in another reaction vessel, 50.0 parts by mass of deionized water, 1.6 parts by mass of a surfactant (Neopelex G-65, manufactured by Kao Co., Ltd.) and 3.0 parts by mass of N-methylolacrylamide (NMAM) were added and stirred. The preemulsion was prepared by putting and stirring the solution which mixed 92.0 mass parts of benzyl methacrylate (BzMA) and 5.0 mass parts of methacrylic acid (MAA) further.

Next, 10.0 mass parts of 2 mass % ammonium persulfate aqueous solution and 10.0 mass parts of 2 mass % ammonium hydrogencarbonate aqueous solution were added, maintaining the internal temperature of a reaction container at 80 degreeC. After 5 minutes, the total amount of the pre-emulsion prepared above, 40.0 parts by mass of a 2% by mass aqueous solution of ammonium persulfate and 40.0 parts by mass of a 2% by mass aqueous solution of ammonium bicarbonate were added uniformly over 4 hours, followed by polymerization. After aging the obtained polymer at 80°C for 2 hours and then cooling to room temperature, pH was adjusted with an appropriate amount of aqueous ammonia solution to obtain an aqueous dispersion of (meth)acrylic resin having a pH of 8.5. Solid content of the obtained (meth)acrylic resin aqueous dispersion was 20.5 mass %. In addition, when the average primary particle diameter of the resin particle in the (meth)acrylic resin aqueous dispersion was measured by the method mentioned above, the average primary particle diameter of the resin particle was 94 nm.

Moreover, this polymerization method is seed polymerization which made seed particle|grains the resin 2 for seeds which is a (meth)acrylic resin.

(Example 1)

[Preparation of coating liquid of water dispersion type resin composition]

The aqueous dispersion containing the (meth)acrylic resin obtained in Production Example 1 and the crosslinking agent were mixed in the mixing ratio shown in Table 1 to prepare a coating solution for the aqueous dispersion type resin composition.

[evaluation]

(1) Suppression of occurrence of rainbow marks

(1-1) Preparation of test pieces

The density|concentration of the coating liquid of the water dispersion type resin composition was prepared so that the thickness after drying might be set to 100 micrometers. The obtained coating solution was coated on a 21 cm x 30 cm size PET separator film (manufactured by Fujimori Kogyo Co., Ltd., Film Viner 100E-0010NO23 (product name)) using a doctor blade, and dried at room temperature for 10 hours. What heat-treated the obtained dry coating film at 180 degreeC for 1 minute with a hot-air circulation dryer (SPEC Co., Ltd. product, HIGH-TEMP-OVEN PHH-200) was used as the test piece.

(1-2) Measurement of refractive index

The prepared test piece was used as a measurement sample, and the refractive index was measured with an Abbe refractometer (manufactured by ATAGO, NAR-1T) using 1-bromonaphthalene as an intermediate solution. The obtained refractive index was evaluated according to the following evaluation criteria. A result is shown in Table 1.

<Evaluation criteria>

A: It is 1.5650 or more and 1.6240 or less, and it is possible to suppress generation|occurrence|production of a rainbow mark effectively.

B: 1.5600 or more and less than 1.5650 or more than 1.6240 and 1.6300 or less, and it is possible to suppress generation|occurrence|production of a rainbow mark slightly.

C: Less than 1.5600 or more than 1.6300, it is difficult to suppress the occurrence of rainbow marks, and there is a practical problem.

(2) Easy adhesion to the hard coat layer

(2-1) Preparation of test piece with hard coat layer

Apply the coating solution of the aqueous dispersion resin composition prepared at an arbitrary concentration on an untreated PET film (Toray Co., Ltd., Lumir 188T-60, thickness 188 μm) with a size of 21 cm × 30 cm using a wire bar so that the film thickness after drying becomes 100 nm. was applied. What heat-treated the obtained coating film at 180 degreeC for 1 minute with a hot-air circulation dryer (SPEC Co., Ltd. product, HIGH-TEMP-OVEN PHH-200) was used as the test piece.

A UV curable hard coat (HX-1000UV manufactured by Kyoeisha Chemical Co., Ltd.) was applied on the surface of the test piece prepared so that the film thickness after drying was 5.0 μm using a wire bar, and a hot air circulation dryer (SPEC Co., Ltd.) ) Product HIGH-TEMP-OVEN PHH-200) was heat-treated at 100°C for 1 minute. Thereafter, using an ultraviolet lamp having an irradiation intensity of 120 W/cm, UV irradiation was performed at an accumulated light amount of about 500 mJ/cm 2 , and the hard coat layer was cured to form a cured film, as a test piece with a hard coat layer.

(2-2) Crosscut Test

Based on JIS-K-5600-5-6 (1999), the crosscut test was done by the following method.

On the surface of the test piece with the hard coat layer prepared above, 11 cuts having a depth reaching the base material at intervals of 1 mm in width and length were made in each direction and cross-cut. The total number of crosscuts is 100.

After affixing a cellophane tape (Nichiban Co., Ltd. Cellotape (registered trademark) CT405AP) having a width of 18 mm on the cross-cut surface, peeling was performed in a 90° direction, and the number of remaining cured films was measured.

The measurement was performed three times, and the average value of the three measurements was evaluated according to the following evaluation criteria.

<Evaluation criteria>

A: The number of the remaining cured films is 100, and it is excellent in easy adhesiveness.

B: The number of the remaining cured films is 80 or more and less than 100, and is slightly excellent in easy adhesiveness.

C: The number of the remaining cured films is 60 or more and less than 80, and easy adhesiveness is inferior, and there exists a hindrance in practical use.

D: The number of the remaining cured films is less than 60, and easy adhesiveness is very inferior, and there exists a hindrance in practical use.

(3) Easy adhesion to the prism layer

(3-1) Preparation of specimen with prism layer attached

Apply the coating solution of the aqueous dispersion resin composition prepared at an arbitrary concentration on an untreated PET film (Toray Co., Ltd., Lumir 188T-60, thickness 188 μm) with a size of 21 cm × 30 cm using a wire bar so that the film thickness after drying becomes 100 nm. was applied. What heat-treated the obtained coating film at 180 degreeC for 1 minute with the hot air circulation dryer (SPEC Co., Ltd. product, HIGH-TEMP-OVEN PHH-200) was used as the test piece.

UV-curable prism resin (CHEM-MAT TECHNOLOGIES CO., LTD., UV9895AS) is applied to the mold for prism molding (pitch 50μm, depth 25μm), and the test piece is fitted so that the surface of the coating film of the test piece overlaps thereon, and a roll laminator is applied. was used for compression. Thereafter, using an ultraviolet lamp having an irradiation intensity of 120 W/cm, UV irradiation was performed at an accumulated light amount of about 500 mJ/cm 2 , and the prism layer was cured to form a cured film. After hardening, the prism film obtained by pulling it off from the mold for prism shaping|molding was used as the test piece with a prism layer.

(3-2) Measurement (Cross Skirt Test)

Based on JIS-K-5600-5-6 (1999), the crosscut test was done by the following method.

On the surface of the test piece with the prism layer prepared above, 11 cuts having a depth reaching the base material at intervals of 1 mm in each direction were cross-cut. The total number of crosscuts is 100. After affixing a cellophane tape (Nichiban Co., Ltd. product, Cellotape (registered trademark) CT405AP) having a width of 18 mm on the cross-cut surface, peeling was performed in a 90° direction to measure the number of remaining cured films.

The measurement was performed three times, and the average value of the three measurements was evaluated according to the following evaluation criteria.

<Evaluation criteria>

A: The number of the remaining cured films is 100, and it is excellent in easy adhesiveness.

B: The number of the remaining cured films is 80 or more and less than 100, and is slightly excellent in easy adhesiveness.

C: The number of the remaining cured films is 60 or more and less than 80, and easy adhesiveness is inferior, and there exists a hindrance in practical use.

D: The number of the remaining cured films is less than 60, and easy adhesiveness is very inferior, and there exists a hindrance in practical use.

(Examples 2-16, Examples 18-20, Comparative Examples 4 and 5)

Except having changed the composition of Example 1 to the composition shown in Table 1, it carried out similarly to Example 1, and the coating liquid of the water dispersion type resin composition as shown in Table 1 was prepared. Various test pieces were produced in the same manner as in Example 1 using the prepared coating liquid of the aqueous dispersion type resin composition. About the obtained test piece, it carried out similarly to Example 1, and each evaluation was performed. A result is shown in Table 1.

(Example 17)

An aqueous dispersion containing the (meth)acrylic resin obtained in Production Example 17, a polyester resin (Z-687), and a crosslinking agent were mixed in the mixing ratio shown in Table 1 to prepare a coating solution of a water dispersion type resin composition. A test piece was produced in the same manner as in Example 1 using the prepared coating liquid of the aqueous dispersion type resin composition. About the obtained test piece, it carried out similarly to Example 1, and each evaluation was performed. A result is shown in Table 1.

(Comparative Example 1)

The aqueous dispersion containing the (meth)acrylic resin obtained in Production Example 20 and the crosslinking agent were mixed in the mixing ratio shown in Table 1 to obtain a coating solution of the aqueous dispersion type resin composition. Various test pieces were produced in the same manner as in Example 1 using the prepared coating liquid of the aqueous dispersion type resin composition. About the obtained test piece, it carried out similarly to Example 1, and each evaluation was performed. A result is shown in Table 1.

(Comparative Example 2)

A polyester resin (Z-687) and a crosslinking agent were mixed in the mixing ratio shown in Table 1 to prepare a coating solution of a water dispersion type resin composition. Various test pieces were produced in the same manner as in Example 1 using the prepared coating liquid of the aqueous dispersion type resin composition. About the obtained test piece, it carried out similarly to Example 1, and each evaluation was performed. A result is shown in Table 1.

(Comparative Example 3)

An aqueous dispersion containing the (meth)acrylic resin obtained in Production Example 20, a polyester resin (Z-687) and a crosslinking agent were mixed in the mixing ratio shown in Table 1 to prepare a coating solution of a water dispersion type resin composition. Various test pieces were produced in the same manner as in Example 1 using the prepared coating solution of the aqueous dispersion type resin composition. About the obtained test piece, it carried out similarly to Example 1, and each evaluation was performed. A result is shown in Table 1.

The abbreviations in Table 1 are as follows. In addition, the number of mass parts in Table 1 is the conversion value of solid content or an active ingredient. "-" in Table 1 shows that the said component is not included.

In addition, the blend resin means the resin component added after seed polymerization.

BzMA: benzyl methacrylate

BzA: benzyl acrylate

PHEMA: phenoxyethyl methacrylate

PHEA: phenoxyethyl acrylate

·EA: ethyl acrylate

MMA: methyl methacrylate

MAA: methacrylic acid

NMAM: N-methylolacrylamide

Z-687: polyethylene naphthalate (PEN) (component: polyester resin containing naphthalene skeleton, active ingredient: 25%, molecular weight: about 26,000, manufactured by Koh Chemical Industries, Ltd., plastic Z-687 (product name))

TWX-797: polyethylene naphthalate (PEN) (component: polyester resin containing naphthalene skeleton, active ingredient: 25%, molecular weight: about 20,000, Takamatsu Oil Co., Ltd. product, Fesresin TWX-797 (product name))

G-65: Anionic emulsifier (ingredient: sodium dodecylbenzenesulfonate, active ingredient: 65%, Kao Co., Ltd. product, Neopelex G-65 (product name))

EA-197D: nonionic emulsifier (component: polyoxyethylene distyrene phenyl ether, active ingredient: 60%, Daiichi Kogyo Pharmaceutical Co., Ltd., Neugen EA-197D (product name))

MW-12LF: Melamine crosslinking agent (ingredient: methylolated melamine resin, active ingredient: 70%, Sanwa Chemical Co., Ltd. product, Nikarac MW-12LF (product name))

WS-500: oxazoline crosslinking agent (component: oxazoline group-containing acrylic polymer, active ingredient: 40%, Nippon Catalyst Co., Ltd., Epocross (registered trademark) WS-500 (product name))

In Comparative Example 1, which does not include a polyester resin, the easy adhesion to the hard coat layer is excellent, but the easy adhesion to the prism layer is poor. In Comparative Example 2, which does not contain (meth)acrylic resin, the easy adhesion to the prism layer is good, but the easy adhesion to the hard coat layer is poor. In Comparative Example 3, the (meth)acrylic resin and the polyester resin are separately polymerized and then a blend resin obtained by mixing each is used, so the easy adhesion to the hard coat layer and the prism layer is poor. In Comparative Example 4, since the (meth)acrylic resin is polymerized as a nucleus in the seed polymerization, the easy adhesion to the hard coat layer is excellent, but the easy adhesion to the prism layer is very poor, and a sufficient refractive index cannot be obtained. In the comparative example 5, since the content rate of the structural unit derived from the aryl group containing monomer with respect to all the structural units of (meth)acrylic resin is less than 60 mass %, sufficient refractive index cannot be obtained.

Examples 1 to 20 contain a (meth)acrylic resin and a polyester resin, and the (meth)acrylic resin includes a structural unit derived from a vinyl-based monomer having an aryl group, and is based on the total mass of the total structural unit. The content of the structural unit derived from the vinyl-based monomer having an aryl group is 60% by mass or more, and a water-dispersible resin composition obtained by polymerizing the monomers constituting the (meth)acrylic resin in the presence of the polyester resin and an aqueous medium is used. Since it is an easily adhesive layer formed by doing so, it is possible to obtain a suitable refractive index to the extent that the occurrence of rainbow marks is suppressed, and even when a hard coat layer and a prism layer are applied, the easy adhesion to both the functional layer and the base material is excellent.

In particular, Examples 1 to 3, 5, 7, 11 and 18 can obtain a refractive index of a degree to suppress the occurrence of rainbow marks, and even when a hard coat layer and a prism layer are applied, it is easy for both the functional layer and the base material Excellent adhesion.

From the above, it can be seen that the easily adhesive layer formed of the water-dispersible resin composition of the present invention has a high refractive index, and has good easy adhesion to both the functional layer and the base material regardless of the material of the functional layer applied.

Claims (10)

Contains (meth)acrylic resin and polyester resin,
The (meth)acrylic resin includes a structural unit derived from a vinyl-based monomer having an aryl group, and the content of the structural unit derived from the vinyl-based monomer having an aryl group with respect to the total mass of all structural units is 60% by mass or more. ,
A water-dispersible resin composition obtained by seed polymerization of a monomer constituting the (meth)acrylic resin in the presence of the polyester resin and water using a polyester resin as seed particles. The method according to claim 1,
The polyester resin is a water-dispersible resin composition having a naphthalene skeleton. The method according to claim 1 or 2,
The content ratio of the (meth)acrylic resin to the polyester resin is 30/70 to 90/10 by mass based on the water dispersion type resin composition. The method according to claim 1 or 2,
The weight average molecular weight of the polyester resin is a water dispersion type resin composition of 5,000 to 100,000. The method according to claim 1 or 2,
The polyester resin is a water-soluble or water-dispersible water-dispersible resin composition. The method according to claim 1 or 2,
The (meth)acrylic resin further includes a structural unit derived from a monomer having a carboxyl group and a structural unit derived from a monomer having a methylol group, and is derived from a monomer having a carboxyl group with respect to the total mass of all structural units. The content rate of the unit is 0.5 mass % - 15 mass %, and the content rate of the structural unit derived from the monomer which has the said methylol group with respect to the total mass of all structural units is 0.5 mass % - 10 mass %, The water dispersion type resin composition. The method according to claim 1 or 2,
A water-dispersible resin composition having a glass transition temperature of 30°C to 120°C of the (meth)acrylic resin. The method according to claim 1 or 2,
A water dispersion type resin composition further comprising a crosslinking agent. An easily adhesive film having a base material and an easily adhesive layer formed using the water-dispersible resin composition according to claim 1 or 2. Including a step of seed polymerization of the monomer constituting the (meth)acrylic resin in the presence of a polyester resin and water, using the polyester resin as seed particles, including a structural unit derived from a vinyl monomer having an aryl group, A water-dispersible resin composition for producing a water-dispersible resin composition containing a (meth)acrylic resin and a polyester resin in which the content of the constituent units derived from the vinyl-based monomer having an aryl group with respect to the total mass of the constituent units is 60% by mass or more manufacturing method.