WO2016159175A1

WO2016159175A1 - Polymer particles, method for producing polymer particles, and use of same

Info

Publication number: WO2016159175A1
Application number: PCT/JP2016/060550
Authority: WO
Inventors: 原田　良祐
Original assignee: 積水化成品工業株式会社
Priority date: 2015-03-31
Filing date: 2016-03-30
Publication date: 2016-10-06
Also published as: CN107406547B; KR101947402B1; JP6550456B2; KR20170131539A; CN107406547A; JPWO2016159175A1

Abstract

Provided are polymer particles capable of being uniformly dispersed in a hydrophilic solvent, such as an alcohol solvent or the like, and having appropriate aggregability, a method for producing such polymer particles, and the use thereof. The polymer particles contain at least one of a constituent unit derived from a monofunctional (meth)acrylic monomer and a constituent unit derived from a monofunctional styrene monomer, a constituent unit derived from a hydroxyl group-containing monomer represented by general formula (1) (in the formula, R¹ represents a hydrogen atom or a methyl group, R² represents an optionally substituted divalent cyclic hydrocarbon group, m and n each independently represent an integer of 0-4, and R³ represents an ester group or ether group having any orientation), and a constituent unit derived from a crosslinkable monomer, and has a hydroxyl value of 5.0-30 mgKOH/g.

Description

POLYMER PARTICLE, METHOD FOR PRODUCING POLYMER PARTICLE, AND USE THEREOF

The present invention relates to polymer particles that can be used as raw materials for optical members such as antiglare films and light diffusing films, methods for producing such polymer particles, and uses thereof (using such polymer particles). Liquid dispersion, optical film, paint, molding material, and optical member).

Polymer particles are used in a wide range of fields such as liquid crystal spacers, chromatographic fillers, and diagnostic reagents. Moreover, it is used also in the field | area of various apparatuses, such as a display apparatus, as optical members, such as a light diffusing plate, a light diffusing film, and an anti-glare film. When such polymer particles are used in actual applications, a dispersion in which the polymer particles are dispersed in a solvent such as water or an organic solvent, or a resin component such as a binder resin is further added to the dispersion. Often used in the form of paint.

In an optical member used for a display device, for example, an antiglare film requires a reflection preventing function. The anti-reflection function is realized by scattering external light by fine irregularities formed by polymer particles. In particular, in order to realize a high-quality reflection preventing function, it is required to form uniform and fine irregularities on the entire antiglare film.

In forming fine irregularities, first, polymer particles are uniformly dispersed in a dispersion containing a solvent and a binder resin without agglomeration. And a dispersion liquid is apply | coated to the surfaces, such as a film base material, and it dries and volatilizes a solvent. Thereby, the polymer particles gather on the film substrate and form a pseudo aggregated state, thereby forming fine irregularities.

As such polymer particles, Patent Document 1 discloses self-aggregating polymer particles. Patent Document 2 discloses highly hydrophilic polymer particles obtained by absorbing and polymerizing a polymerizable vinyl-based monomer into seed particles containing a hydrophilic macromonomer as polymer particles having excellent dispersibility. It is disclosed.

JP 2013-231133 A JP 2012-062389 A

However, the quality of optical films such as anti-glare films has been diversified along with the recent high definition and thinning of display devices. In some cases, an organic solvent may be used. For this reason, the polymer particles may be required to be uniformly dispersed in a hydrophilic solvent such as an alcohol solvent. Therefore, development of polymer particles that can be uniformly dispersed in a hydrophilic solvent such as an alcohol solvent and can be sufficiently aggregated after coating is desired.

The present invention has been made in view of the above problems, and the object thereof is a polymer particle that can be uniformly dispersed in a hydrophilic solvent such as an alcohol-based solvent and has an appropriate cohesiveness, and its It is an object of the present invention to provide a method for producing such polymer particles and use thereof (a dispersion using such polymer particles, an optical film, a paint, a molding material, and an optical member).

In order to solve the above problems, the polymer particles of the present invention include at least one of a structural unit derived from a monofunctional (meth) acrylic monomer and a structural unit derived from a monofunctional styrene monomer. The following general formula (1)

(In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent cyclic hydrocarbon group which may have a substituent, and m and n are each independently 0-4. R ³ represents the following formulas (2) to (4):

In the above formulas (2) to (4)

Represents the binding position)
And a structural unit derived from a crosslinkable monomer, and a hydroxyl value is 5.0 mgKOH / g or more and 30 mgKOH / g or less. It is said.

The polymer particles having the above structure can be uniformly dispersed in a hydrophilic solvent such as an alcohol solvent when the hydroxyl value is 5.0 mgKOH / g or more and 30 mgKOH / g or less. It has a good cohesiveness. Therefore, for example, when polymer particles are dispersed in a dispersion containing a hydrophilic solvent such as an alcohol solvent and a binder, and the dispersion is applied on a base film, and then the hydrophilic solvent is volatilized, An optical film having uniform characteristics without unevenness can be produced. Further, when the hydrophilic solvent is volatilized after the dispersion is applied on the base film, the uniformly dispersed polymer particles can be appropriately aggregated to form fine irregularities. As a result, it is possible to manufacture an optical film such as an antiglare film having good antiglare properties by scattering external light such as light emitted from an external fluorescent lamp and preventing reflection.

The method for producing polymer particles of the present invention is a method for producing polymer particles by polymerizing vinyl monomers to produce polymer particles, wherein the vinyl monomers are monofunctional (meth) acrylic. At least one of a monomer and a monofunctional styrene monomer, and the following general formula (1)

In the above formulas (2) to (4)

Represents the binding position)
And the vinyl monomer contains the hydroxyl group-containing monomer in a range of 2 mol% or more and less than 20 mol%. It is said.

According to the above method, the vinyl monomer is uniformly dispersed in a hydrophilic solvent such as an alcohol solvent by including the hydroxyl group-containing monomer in a range of 2 mol% or more and less than 20 mol%. In addition, it is possible to obtain polymer particles having appropriate cohesiveness. Therefore, for example, when polymer particles are dispersed in a dispersion containing a hydrophilic solvent such as an alcohol solvent and a binder, and the dispersion is applied on a base film, and then the hydrophilic solvent is volatilized, An optical film having uniform characteristics without unevenness can be produced. Further, when the hydrophilic solvent is volatilized after the dispersion is applied on the base film, the uniformly dispersed polymer particles can be appropriately aggregated to form fine irregularities. As a result, an optical film such as an antiglare film having good antiglare properties can be produced.

The dispersion of the present invention contains the polymer particles of the present invention and a binder, and the polymer particles are dispersed in the binder as a dispersoid.

According to the above configuration, even when a hydrophilic solvent such as an alcohol solvent is included, a dispersion liquid in which the polymer particles are uniformly dispersed can be realized.

The optical film of the present invention is characterized in that the dispersion of the present invention is applied on a base film.

In the above configuration, when the dispersion of the present invention is obtained by coating on a substrate film, as described above, even when the dispersion contains a hydrophilic solvent such as an alcohol solvent, Since a dispersion liquid in which the polymer particles are uniformly dispersed can be realized, an optical film having uniform characteristics without unevenness can be realized. In addition, since the polymer particles can be appropriately aggregated to form fine irregularities, an optical film such as an antiglare film having good antiglare properties can be produced.

The paint of the present invention is characterized by containing the polymer particles of the present invention.

According to the above configuration, even when a hydrophilic solvent such as an alcohol solvent is included, a paint in which the polymer particles are uniformly dispersed can be realized.

According to the present invention, polymer particles that can be uniformly dispersed in a hydrophilic solvent such as an alcohol-based solvent and have appropriate cohesiveness, a method for producing such polymer particles, and use thereof ( Dispersions, optical films, paints, molding materials, and optical members using such polymer particles can be provided.

The present invention is described in detail below.
(Polymer particles)
The polymer particles of the present invention comprise at least one of a structural unit derived from a monofunctional (meth) acrylic monomer and a structural unit derived from a monofunctional styrene monomer, and the following general formula (1):

In the above formulas (2) to (4)

Represents the binding position)
The hydroxyl group value is 5.0 mgKOH / g or more and 30 mgKOH / g or less including the structural unit derived from the hydroxyl-containing monomer represented by these, and the structural unit derived from a crosslinkable monomer.

The polymer particles have a hydroxyl value of 5.0 mgKOH / g or more and 30 mgKOH / g or less, so that the polymer particles can be uniformly dispersed in a hydrophilic solvent such as an alcohol-based solvent and have an appropriate aggregation. Have sex. In the case of polymer particles having a hydroxyl value of less than 5.0 mg KOH / g, they are aggregated without being uniformly dispersed in a hydrophilic solvent such as an alcohol solvent. On the other hand, in the case of polymer particles having a hydroxyl value greater than 30 mgKOH / g, the cohesiveness is insufficient. The hydroxyl value is measured by a hydroxyl value quantitative analysis method (JIS K 0070).

The monofunctional (meth) acrylic monomer is a (meth) acrylic monomer having one ethylenically unsaturated group other than the hydroxyl group-containing monomer represented by the general formula (1) (( A compound having a (meth) acryloyl group). Examples of the monofunctional (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic. (Meth) acrylic acid such as tert-butyl acid, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Alkyl etc. are mentioned. In this application document, “(meth) acryl” means acryl or methacryl, “(meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylate” means acrylate or methacrylate. To do.

The monofunctional (meth) acrylic monomer preferably contains a monofunctional (meth) acrylic monomer having a solubility in water of 25 ° C. of 2.00% by weight or less. Thereby, further better cohesion can be imparted to the polymer particles. Therefore, for example, when polymer particles are dispersed in a dispersion containing a solvent and a binder and applied on a base film, the polymer particles form irregularities of good size when the solvent is volatilized. Since it can suppress, optical films, such as an anti-glare film, with a further favorable anti-glare property can be manufactured.

As the monofunctional (meth) acrylic monomer having a solubility in water of 25 ° C. or less of 2.00% by weight, specifically, methyl methacrylate (the solubility in water at 25 ° C. is 1.72% by weight). ), Ethyl (meth) acrylate, n-butyl (meth) acrylate (sodium n-butyl methacrylate has a solubility in water at 25 ° C. of 0.04% by weight), isobutyl (meth) acrylate, (meth) acrylic acid alkyl (meth) acrylates such as tert-butyl, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Etc.

In addition, in this application document, the solubility with respect to 25 degreeC water shall be measured with the following method.
(Measurement method of solubility in water at 25 ° C.)
Water and a monofunctional (meth) acrylic monomer are mixed at a weight ratio of 1: 1 and stirred at 25 ° C. for 30 minutes. Next, the aqueous phase and the oil phase are separated using a separatory funnel, and the amount (% by weight) of the monofunctional (meth) acrylic monomer dissolved in the aqueous phase is measured by high performance liquid chromatography (HPLC). To do.

The ratio of the monofunctional (meth) acrylic monomer having a solubility in water at 25 ° C. of 2.00% by weight or less in the monofunctional (meth) acrylic monomer is 50% by weight or more. Preferably, it is 70% by weight or more, and more preferably 90% by weight or more. Thereby, further better cohesion can be imparted to the polymer particles. Therefore, for example, when polymer particles are dispersed in a dispersion liquid containing a solvent and a binder and applied on a base film, and then the solvent is volatilized, the polymer particles form unevenness of a better size. Therefore, it is possible to produce an optical film such as an antiglare film having further improved antiglare properties.

The monofunctional styrene monomer is a styrene monomer (styrene or a derivative thereof) having one ethylenically unsaturated group. Examples of the monofunctional styrene monomer include styrene, α-methyl styrene, vinyl toluene, ethyl vinyl benzene and the like. Among these, styrene is used in view of alcohol solvent dispersibility and polymerization reactivity. preferable.

The hydroxyl group-containing monomer represented by the general formula (1) is a hydroxyl group-containing monomer in which R ³ is a divalent group (ester group) represented by the formula (2), that is, a hydroxyl group-containing (meth). An acrylic ester; a hydroxyl group-containing monomer in which R ³ is a divalent group (ether group) represented by the general formula (3), that is, a hydroxyl group-containing vinyl ether or a hydroxyl group-containing isopropenyl ether; and R ³ is the formula It is a hydroxyl group-containing monomer that is a divalent group (ester group) represented by (4), that is, either a hydroxyl group-containing vinyl ester or a hydroxyl group-containing isopropenyl ester. The hydroxyl group-containing monomer represented by the general formula (1) is a hydroxyl group-containing monomer in which R ³ is a divalent group represented by the formula (2), that is, a hydroxyl group-containing (meth) acrylate ester. Preferably there is. When polymer particles are produced by seed polymerization using a hydroxyl group-containing (meth) acrylic acid ester as the hydroxyl group-containing monomer represented by the general formula (1), the polymer particles can be made more monodisperse. it can. Moreover, the polymer particle containing the structural unit derived from a hydroxyl-containing (meth) acrylic acid ester as a hydroxyl-containing monomer represented by the said General formula (1) is used for optical members, such as a glare-proof film and a light-diffusion film. Then, the optical characteristics such as antiglare property and light diffusibility of the optical member can be improved.

In the general formula (1), the divalent cyclic hydrocarbon group which may have a substituent represented by R ² is a divalent alicyclic hydrocarbon which may have a substituent. Group or an aromatic hydrocarbon group. Examples of the substituent that the divalent alicyclic hydrocarbon group or aromatic hydrocarbon group may have include a hydroxyl group, an alkyl group (particularly an alkyl group having 1 to 3 carbon atoms), an alkoxy group (particularly, An alkoxy group having 1 to 3 carbon atoms), a halogen group, a halogenated alkyl group (particularly a halogenated alkyl group having 1 to 3 carbon atoms), or a hydroxyalkyl group (particularly a hydroxyalkyl group having 1 to 3 carbon atoms). It is done.

Of the hydroxyl group-containing (meth) acrylic acid ester represented by the general formula (1), a hydroxyl group-containing (meth) acrylic acid in which R ² is a divalent alicyclic hydrocarbon group which may have a substituent. the ester, for example, R ² is a hydroxyl group-containing (meth) acrylic acid esters, optionally adamantanediyl group optionally R ² is substituted it is good cyclohexane diyl group which may have a substituent hydroxyl group Containing (meth) acrylic acid ester, hydroxyl group-containing (meth) acrylic acid ester in which R ² is a cyclodecanediyl group, hydroxyl group-containing (meth) acrylic acid ester in which R ² is a norbornanediyl group, R ² is tetracyclo [4. 4.0.1 ^2,5 . 1, ¹⁰ ] hydroxyl group-containing (meth) acrylic acid ester which is a dodecanediyl group, R ² is hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . And a hydroxyl group-containing (meth) acrylic acid ester which is a ^09,14 ] heptadecandiyl group.

Examples of the hydroxyl group-containing (meth) acrylic acid ester represented by the general formula (1) in which R ² is a cyclohexanediyl group optionally having a substituent include 1,4-cyclohexanedimethanol mono (meth) acrylate. , Cyclohexanediol mono (meth) acrylate, 4-hydroxymethylcyclohexylethyl (meth) acrylate, 3-hydroxymethylcyclohexylethyl (meth) acrylate, 4-hydroxymethylcyclohexylpropyl (meth) acrylate, 3-hydroxymethylcyclohexylpropyl (meth) ) Acrylate, 4-hydroxymethylcyclohexylbutyl (meth) acrylate, 3-hydroxymethylcyclohexylbutyl (meth) acrylate, 3,4-dihydroxycyclohexylmethyl (meth) acrylate Examples thereof include acrylate, 3,4-dihydroxycyclohexylethyl (meth) acrylate, and 3,4-dihydroxycyclohexylpropyl (meth) acrylate.

Examples of the hydroxyl group-containing (meth) acrylic acid ester represented by the general formula (1) in which R ² is an adamantanediyl group which may have a substituent include 3-hydroxy-1-adamantyl (meth) acrylate ( Also known as: 1,3-adamantanediol mono (meth) acrylate), 1,3,5-adamantanetriol mono (meth) acrylate, 3,5,7-trihydroxy-1-adamantyl (meth) acrylate, 5,7- Dimethyl-3-hydroxy-1-adamantyl (meth) acrylate, 5-methoxy-3-hydroxy-1-adamantyl (meth) acrylate, 5-ethoxy-3-hydroxy-1-adamantanyl (meth) acrylate, (meth) Acrylic Royloxy- (1- (3-hydroxymethyl) adamantyl) methane etc. Is mentioned.

Examples of the hydroxyl group-containing (meth) acrylic acid ester represented by the general formula (1) where R ² is a cyclodecanediyl group include tricyclodecane dimethanol monoacrylate.

Examples of the hydroxyl group-containing (meth) acrylic acid ester represented by the general formula (1) where R ² is a norbornanediyl group include 2,5-norbornanedimethanol mono (meth) acrylate and 2,6-norbornanedimethanol mono (Meth) acrylate, 2-hydroxymethylbicyclo [2.2.1] hept-5-yl (meth) acrylate, 2-hydroxymethylbicyclo [2.2.1] hept-6-yl (meth) acrylate, 2 -Hydroxyethylbicyclo [2.2.1] hept-5-yl acrylate, 2-hydroxyethylbicyclo [2.2.1] hept-6-yl acrylate and the like.

Represented by the general formula (1), R ² is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] As the hydroxyl group-containing (meth) acrylic acid ester which is dodecanediyl group, e.g., 3-hydroxymethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-8-yl (meth) acrylate, 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-9-yl (meth) acrylate, 3-hydroxyethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-yl acrylate, 3-hydroxyethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-9-yl acrylate and the like.

Represented by the general formula (1), R ² is hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] As the hydroxyl group-containing (meth) acrylic acid ester which is heptadecane-diyl group, for example, 4-hydroxymethyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-yl (meth) acrylate, 4-hydroxymethyl-et-methylhexahydrophthalic cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] heptadec-4-yl acrylate.

Commercially available products of these hydroxyl group-containing (meth) acrylic acid esters include 1,4-cyclohexanedimethanol monoacrylate manufactured by Nippon Kasei Co., Ltd., HADM (3-hydroxy-1-adamantyl methacrylate) manufactured by Mitsubishi Gas Chemical Co., Ltd., Examples thereof include HADA (3-hydroxy-1-adamantyl acrylate), DHADM (1,3,5-adamantanetriol monomethacrylate), HQMA (cyclohexanediol monomethacrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd.

Of the hydroxyl group-containing (meth) acrylate ester represented by the general formula (1), a hydroxyl group-containing (meth) acrylate ester in which R ² is a divalent aromatic hydrocarbon group which may have a substituent. Examples thereof include 4-hydroxyphenyl acrylate (commercially available from BOC Sciences), 4-hydroxyphenyl methacrylate (commercially available from Showa Denko KK), and the like.

Examples of the hydroxyl group-containing vinyl ether or hydroxyl group-containing isopropenyl ether represented by the general formula (1) include cyclohexane dimethanol monovinyl ether (commercially available from Nippon Carbide Industries Co., Ltd.), 1,4-cyclohexanediol monovinyl ether (JP-A-5 -186383)). These hydroxyl group-containing monomers represented by the general formula (1) may be used alone or in combination of two or more.

The polymer particles of the present invention preferably contain a constituent unit derived from the hydroxyl group-containing monomer in a range of 2 mol% or more and less than 20 mol%. When the structural unit derived from the hydroxyl group-containing monomer is less than 2 mol%, the dispersibility in a hydrophilic solvent such as an alcohol solvent is insufficient. Therefore, for example, when polymer particles are dispersed in a dispersion containing a hydrophilic solvent such as an alcohol solvent and a binder, and the dispersion is applied onto a substrate film, an optical film is produced uniformly. There is a possibility that an optical film having various characteristics cannot be obtained. On the other hand, when the structural unit derived from the hydroxyl group-containing monomer is 20 mol% or more, the cohesiveness of the polymer particles may be too high. For this reason, for example, when polymer particles are dispersed in a dispersion containing a solvent and a binder, the polymer particles may be aggregated and a dispersion capable of being applied may not be obtained.

The crosslinkable monomer is a polyfunctional monomer having a plurality of ethylenically unsaturated groups, and has a function as a crosslinking agent. Examples of the crosslinkable monomer include trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and decaethylene glycol di (meth). ) Acrylate, pentadecaethylene glycol di (meth) acrylate, pentacontactor ethylene glycol di (meth) acrylate, 1,3-butylene di (meth) acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta And polyfunctional (meth) acrylic monomers such as erythritol tetraacrylate; divinyl monomers such as divinylbenzene, divinylnaphthalene and N, N-divinylaniline.

The polymer particles of the present invention preferably contain 3 to 50% by weight of structural units derived from the crosslinkable monomer. When the structural unit derived from the crosslinkable monomer is less than 3% by weight, the degree of crosslinking of the polymer particles is lowered, and the solvent resistance of the polymer particles is lowered. As a result, for example, when the polymer particles are dispersed in an organic solvent and a binder and applied as a dispersion, the polymer particles swell and the viscosity of the dispersion increases, and the workability of the coating decreases. There is a fear. Moreover, when there are more structural units derived from the said crosslinkable monomer than 50 weight%, the improvement corresponding to the usage-amount of the said crosslinkable monomer is not recognized, but production cost may rise.

The volume average particle diameter of the polymer particles of the present invention is preferably 0.2 to 100 μm. When the polymer particles of the present invention are used for an antiglare film or the like, the volume average particle diameter is preferably 10 μm or less. When the volume average particle size is 10 μm or less, polymer particles are dispersed in a dispersion containing a solvent and a binder and applied onto a base film, and then the solvent is volatilized and then aggregated in an appropriate quantity. Thus, a convex portion having a preferable size can be formed. Therefore, for example, an optical film such as an antiglare film having better antiglare properties can be produced. The polymer particles of the present invention preferably have a volume average particle size of 0.5 μm or more and 10 μm or less. Thereby, when a polymer particle is disperse | distributed in the dispersion liquid containing a solvent and a binder and it apply | coats on a base film, and a solvent is volatilized, the convex part of a more preferable size can be formed. Therefore, for example, an optical film such as an antiglare film having better antiglare properties can be produced.

In the case where the volume average particle diameter of the polymer particles is larger than 10 μm, for example, an optical film is prepared by applying a dispersion obtained by dispersing polymer particles in a binder on a base film. When the film is arranged as an antiglare film on the surface of the display device, the convex portions formed by the aggregation of polymer particles become steep, so that the outside light is scattered too much and the display surface becomes whitish. There is a fear. In the case of polymer particles used in an antiglare film for a higher definition display, the volume average particle diameter is more preferably 5.0 μm or less. Further, when the volume average particle diameter of the polymer particles is smaller than 0.5 μm, for example, an optical film is produced by applying a dispersion obtained by dispersing polymer particles in a binder on a base film, When the optical film is arranged as an antiglare film on the surface of the display device, the convex portions formed by the aggregation of the polymer particles become flat, so that it is not possible to scatter external light and to the display surface. There is a risk that it will be impossible to suppress the reflection of.

The polymer particles of the present invention preferably have a volume average particle diameter of 0.8 to 50 μm when used in paints and the like. When the volume average particle diameter of the polymer particles is within the above range, when used in a coating, the polymer particles tend to exhibit sufficient matting properties, and the particles are less likely to fall off from the coating film, which is preferable. .

The coefficient of variation (CV) of the particle diameter of the polymer particles is preferably 35% or less. When polymer particles are used for an optical member such as an antiglare film or a light diffusion film, the coefficient of variation (CV) of the particle diameter of the polymer particles is more preferably 15% or less. Thereby, when polymer particles are used for an optical member such as an antiglare film or a light diffusing film, optical properties such as antiglare property and light diffusibility of the optical member can be improved. When polymer particles are used in a paint or the like, the coefficient of variation (CV) of the particle diameter of the polymer particles is more preferably 15 to 35%. When it is in the above range, it is easy to exhibit a sufficient matting property.

Analytical methods such as gas chromatography, liquid chromatography, infrared spectroscopy (IR), and nuclear magnetic resonance spectroscopy (NMR) are used for quantification and qualification of the structural unit derived from each monomer in the polymer particles. This can be confirmed. The weight ratio of each monomer in the monomer mixture and the weight ratio of the structural unit derived from each monomer in the polymer particles are substantially the same.

[Production method of polymer particles]
Next, a method for producing polymer particles according to the present invention will be described.
The method for producing polymer particles according to the present invention is a method for producing polymer particles by polymerizing a vinyl monomer to produce polymer particles, wherein the vinyl monomer is monofunctional (meth). At least one of an acrylic monomer and a monofunctional styrene monomer, and the following general formula (1)

In the above formulas (2) to (4)

Represents the binding position)
The vinyl monomer is a method containing the hydroxyl group-containing monomer in a range of 2 mol% or more and less than 20 mol%. .

The polymerization of the vinyl monomer is preferably seed polymerization performed by absorbing the vinyl monomer in seed particles in an aqueous medium. Thereby, the dispersion | variation in the particle diameter of the polymer particle obtained can be suppressed. Improve optical properties such as antiglare and light diffusivity of optical film when polymer particles are used in optical films such as antiglare film and light diffusing film by suppressing variation in particle diameter Is possible. However, the production of the polymer particles according to the present invention is not necessarily limited to seed polymerization, and can also be performed by a polymerization method such as emulsion polymerization or suspension polymerization.

[Seed polymerization]
Next, the seed polymerization will be described in detail.
Seed polymerization is performed using seed (seed) particles made of a polymer obtained by polymerizing a monomer, preferably a vinyl monomer (hereinafter referred to as “vinyl monomer for seed particles”). Specifically, for seed polymerization in which the vinyl monomer (hereinafter referred to as “vinyl monomer for seed polymerization”) is absorbed in seed particles in an aqueous medium and absorbed. This vinyl monomer is polymerized in seed particles.

The vinyl monomer for seed particles may be a compound having at least one ethylenically unsaturated group. For example, the monofunctional (meth) acrylic monomer described above, the monofunctional styrene monomer described above, and the like. Examples thereof include a monomer, a hydroxyl group-containing monomer represented by the aforementioned general formula (1), and the aforementioned crosslinkable monomer. The vinyl monomer for the seed particles preferably contains at least one of a monofunctional (meth) acrylic monomer and a monofunctional styrene monomer. That is, the seed particle preferably includes at least one of a structural unit derived from a monofunctional (meth) acrylic monomer and a structural unit derived from a monofunctional styrene monomer. The seed particles are derived from non-crosslinked polymer particles that do not contain a structural unit derived from a crosslinkable monomer or a crosslinkable monomer so as to easily absorb the vinyl monomer for seed polymerization. Preference is given to finely crosslinked polymer particles containing a trace amount of structural units.

The vinyl monomer for seed polymerization may be a compound having at least one ethylenically unsaturated group. For example, the monofunctional (meth) acrylic monomer described above and the monofunctional styrene described above. Examples thereof include system monomers and the aforementioned crosslinkable monomers. The vinyl monomer for seed polymerization contains at least one of the monofunctional (meth) acrylic monomer and monofunctional styrene monomer described above, and a hydroxyl group represented by the general formula (1) described above. It is preferable to contain a monomer and the crosslinkable monomer mentioned above.

In seed polymerization, first, seed particles are added to an emulsion (suspension) containing a vinyl monomer for seed polymerization and an aqueous medium.

Examples of the aqueous medium include water; lower alcohols such as methyl alcohol and ethyl alcohol (alcohols having 5 or less carbon atoms); mixtures of water and lower alcohols, and the like.

It is preferable to add a surfactant to the emulsion. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.

Examples of the anionic surfactant include fatty acid soaps such as sodium oleate and castor oil potassium soap; alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyl Dialkylsulfosuccinates such as naphthalenesulfonate, alkanesulfonate, sodium di (2-ethylhexyl) sulfosuccinate, sodium dioctylsulfosuccinate; alkenyl succinate (dipotassium salt); alkyl phosphate ester salt; naphthalenesulfonate formalin Condensate; Polyoxyethylene alkyl phenyl ether sulfate ester salt; Polyoxyethylene alkyl ether sulfate salt such as sodium polyoxyethylene lauryl ether sulfate Polyoxyethylene alkyl sulfates, and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene styrenated phenyl ether, and alkylene groups. Polyoxyalkylene alkyl ethers such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Examples thereof include alkylamines, glycerin fatty acid esters, and oxyethylene-oxypropylene block polymers.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of the amphoteric surfactants include lauryl dimethylamine oxide, phosphate ester surfactants, phosphite ester surfactants, and the like. 1 type may be used for the said surfactant and it may use it in combination of 2 or more type.

The amount of the surfactant used in the seed polymerization is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl monomer for seed polymerization. When the amount of the surfactant used is less than the above range, the polymerization stability may be lowered. Moreover, when the usage-amount of surfactant is more than the said range, the cost for surfactant will deteriorate.

The above emulsion can be prepared by a known method. For example, an emulsion is obtained by adding a vinyl monomer and a surfactant for seed polymerization to an aqueous medium and dispersing the mixture with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer (registered trademark). Can do.

The seed particles may be added to the emulsion as it is, or may be added to the emulsion in a form dispersed in an aqueous medium. After the seed particles are added to the emulsion, the vinyl monomer for seed polymerization is absorbed by the seed particles. This absorption can usually be performed by stirring the emulsion at room temperature (about 20 ° C.) for 1 to 12 hours. Further, the emulsion may be heated to about 30 to 50 ° C. in order to promote the absorption of the vinyl monomer for seed polymerization into the seed particles.

The seed particles swell by absorbing the vinyl monomer for seed polymerization. The mixing ratio of the seed polymerization vinyl monomer and seed particles to be absorbed is within the range of 5 to 300 parts by weight of the seed polymerization vinyl monomer with respect to 1 part by weight of the seed particles. It is preferably within the range of 100 to 250 parts by weight. When the mixing ratio of the vinyl monomer for seed polymerization is smaller than the above range, the increase in particle diameter due to polymerization is small, and thus the production efficiency is lowered. On the other hand, when the mixing ratio of the vinyl monomer for seed polymerization to be absorbed is larger than the above range, the vinyl monomer for seed polymerization is not completely absorbed by the seed particles and is suspended in an aqueous medium independently. Polymerization may produce polymer particles with an unusually small particle size. The end of absorption of the vinyl monomer for seed polymerization into the seed particles can be determined by confirming the expansion of the particle diameter by observation with an optical microscope.

The polymer particles according to the present invention can be obtained by polymerizing the vinyl monomer for seed polymerization absorbed by the seed particles. Note that the polymer particles according to the present invention may be obtained by repeating the process of absorbing and polymerizing the vinyl monomer for seed polymerization into the seed particles a plurality of times.

In seed polymerization, a polymerization initiator may be added to the polymerization reaction system as necessary. The polymerization initiator may be mixed with the vinyl monomer for seed polymerization, and then the resulting mixture may be dispersed in an aqueous medium. The polymerization initiator and the vinyl monomer for seed polymerization These may be mixed separately in an aqueous medium. If the particle size of the droplets of the vinyl monomer for seed polymerization existing in the obtained emulsion is smaller than the particle size of the seed particles, the vinyl monomer for seed polymerization will be smaller. This is preferable because it is efficiently absorbed by the seed particles.

The polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, benzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide Organic peroxides such as oxide, t-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3) 3-trimethylbutyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonite) ), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), (2-carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2 Azo compounds such as 2,2′-azobisisobutyrate. The polymerization initiator is preferably used within a range of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the vinyl monomer for seed polymerization.

The polymerization temperature of the seed polymerization can be appropriately determined according to the type of vinyl monomer for seed polymerization and the type of polymerization initiator used as necessary. Specifically, the polymerization temperature of the seed polymerization is preferably 25 to 110 ° C., more preferably 50 to 100 ° C. The polymerization time for seed polymerization is preferably 1 to 12 hours. The polymerization reaction of the seed polymerization may be performed in an atmosphere of an inert gas (for example, nitrogen) that is inert to the polymerization. The polymerization reaction of the seed polymerization is preferably carried out by raising the temperature after the vinyl monomer for seed polymerization and the polymerization initiator used as necessary are completely absorbed by the seed particles.

In the seed polymerization, a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the polymer particles. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinylpyrrolidone. Moreover, the polymer dispersion stabilizer and an inorganic water-soluble polymer compound such as sodium tripolyphosphate may be used in combination. Of these polymer dispersion stabilizers, polyvinyl alcohol and polyvinyl pyrrolidone are preferred. The addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer for seed polymerization.

Also, in order to suppress the generation of emulsified particles (polymer particles with too small particle size) in the aqueous medium in the above polymerization reaction, nitrites such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble Water-soluble polymerization inhibitors such as vitamin Bs, citric acid and polyphenols may be added to the aqueous medium. The addition amount of the polymerization inhibitor is preferably in the range of 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the vinyl monomer for seed polymerization.

In this way, the polymer particles obtained by polymerizing the vinyl monomer for seed polymerization absorbed by the seed particles have an aqueous medium by centrifugation or filtration as necessary after the completion of the polymerization. It is removed, washed with water and / or solvent and then dried. The drying method is not particularly limited. For example, a spray drying method typified by a spray dryer, a method of drying by adhering to a heated rotating drum typified by a drum dryer, a freeze drying method, etc. The method is mentioned.

The polymerization method for polymerizing the vinyl monomer for seed particles to obtain seed particles is not particularly limited, but dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization, seed polymerization, suspension polymerization are not limited. Turbid polymerization or the like can be used. In order to obtain polymer particles having a substantially uniform particle size by seed polymerization, it is first necessary to use seed particles having a substantially uniform particle size and grow these seed particles substantially uniformly. Seed particles with a substantially uniform particle size as a raw material are produced by polymerizing vinyl monomers for seed particles using polymerization methods such as soap-free emulsion polymerization (emulsion polymerization without using a surfactant) and dispersion polymerization. can do. Therefore, as a polymerization method for obtaining seed particles, emulsion polymerization, soap-free emulsion polymerization, seed polymerization, and dispersion polymerization are preferable.

In the polymerization of the vinyl monomer for seed particles to obtain seed particles, a polymerization initiator is used as necessary. Examples of the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3, 5 , 5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, organic peroxides such as di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, Examples thereof include azo compounds such as 1′-azobiscyclohexanecarbonitrile and 2,2′-azobis (2,4-dimethylvaleronitrile). The polymerization initiator is preferably used in an amount of 0.1 to 3 parts by weight with respect to 100 parts by weight of the vinyl monomer for seed particles. The weight average molecular weight of the obtained seed particles can be adjusted by adjusting the amount of the polymerization initiator used.

In the polymerization for obtaining seed particles, a molecular weight modifier may be used in order to adjust the weight average molecular weight of the obtained seed particles. Examples of the molecular weight modifier include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan; α-methylstyrene dimer; terpenes such as γ-terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride, etc. Can be used. The weight average molecular weight of the obtained seed particles can be adjusted by adjusting the amount of the molecular weight modifier used.

(Suspension polymerization)
Next, suspension polymerization will be described in detail.
Suspension polymerization is a method in which a vinyl monomer (hereinafter referred to as “vinyl monomer for suspension polymerization”) is suspended in an aqueous medium for polymerization. The vinyl monomer for suspension polymerization is the same as the vinyl monomer for seed polymerization described above. In the suspension polymerization, a surfactant, a polymerization initiator, a polymerization inhibitor, a molecular weight adjusting agent, and the like are used as necessary. The aqueous medium, surfactant, polymerization initiator, polymerization inhibitor, molecular weight modifier and the like are the same as those described for seed polymerization or polymerization for obtaining seed particles. In the suspension polymerization, the polymerization conditions (polymerization temperature, polymerization time, etc.), post-treatment (removal of aqueous medium, washing, drying) performed as necessary after the polymerization are the same as in the seed polymerization.

In the suspension polymerization reaction system, a dispersant is used as necessary. Examples of the dispersant include soluble poorly water-soluble inorganic compounds such as calcium phosphate and magnesium pyrophosphate; water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.) and polycarboxylic acids. It is done. Each of the dispersants may be used alone or in combination of two or more. The amount of the dispersant added is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer for suspension polymerization.

[Use of polymer particles]
The polymer particle of the present invention is suitable as a particle that is added to an optical member such as an optical film such as an antiglare film or a light diffusion film to impart antiglare property or light diffusibility to the optical film, It is suitable for use as a dispersion by dispersing in a binder.

[Dispersion]
The dispersion of the present invention contains polymer particles and a binder, and the polymer particles are dispersed as a dispersoid in a dispersion medium such as the binder.

The binder is not particularly limited as long as it is used in the field according to required properties such as transparency, polymer particle dispersibility, light resistance, moisture resistance and heat resistance. Examples of the binder include (meth) acrylic resins; (meth) acrylic-urethane resins; urethane resins; polyvinyl chloride resins; polyvinylidene chloride resins; melamine resins; styrene resins; alkyd resins. Phenol resin; epoxy resin; polyester resin; silicone resin such as alkylpolysiloxane resin; (meth) acrylic-silicone resin, silicone-alkyd resin, silicone-urethane resin, silicone-polyester resin, etc. Modified silicone resins; binder resins such as fluororesins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers.

The binder resin is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction from the viewpoint of improving the durability of the coating dispersion. The curable resin can be cured under various curing conditions. The curable resin is classified into an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, a hot air curable resin, and the like depending on the type of curing.

Examples of the thermosetting resin include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.

As the ionizing radiation curable resin, synthesized from polyfunctional (meth) acrylate resin such as polyhydric alcohol polyfunctional (meth) acrylate; diisocyanate, polyhydric alcohol, and (meth) acrylic acid ester having a hydroxy group And polyfunctional urethane acrylate resins.

As the ionizing radiation curable resin, besides these, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can also be used.

As the binder resin, a thermoplastic resin can be used in addition to the curable resin described above. Thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; vinyl acetate homopolymers and copolymers, vinyl chloride homopolymers and copolymers, and vinylidene chloride alone (Meth) such as vinyl resins such as polymers and copolymers; acetal resins such as polyvinyl formal and polyvinyl butyral; homopolymers and copolymers of acrylate esters, homopolymers and copolymers of methacrylate esters, etc. Examples include acrylic resins; polystyrene resins; polyamide resins; linear polyester resins; polycarbonate resins.

In addition to the binder resin described above, a rubber binder such as synthetic rubber and natural rubber, other inorganic binders, and the like can also be used as the binder. Examples of the rubber binder resin include ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber.

The dispersion liquid may contain an organic solvent as a dispersion medium. The organic solvent is not particularly limited. When the dispersion is used for coating on a substrate such as a substrate film to be described later, the organic solvent is added to the dispersion by adding it to the dispersion. Any material that can be applied easily can be used. Examples of the organic solvent include aromatic solvents such as toluene and xylene; alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene Glycol ethers such as glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol methyl ether; 2-methoxyethyl acetate Salts, glycol ether esters such as 2-ethoxyethyl acetate (cellosolve acetate), 2-butoxyethyl acetate, propylene glycol methyl ether acetate; chlorinated solvents such as chloroform, dichloromethane, trichloromethane, and methylene chloride Ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane and 1,3-dioxolane; amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide and dimethylacetamide can be used. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, alcohol-based solvents having 5 or less carbon atoms are preferable from the viewpoint of uniform dispersibility of the polymer particles in the dispersion and aggregation of the polymer particles after drying. Methanol, ethanol, propanol Is more preferable. Hydrophobic polymer particles are not uniformly dispersed in a dispersion containing a hydrophilic solvent, which is an alcohol solvent having 5 or less carbon atoms, as a dispersion medium, but the polymer particles of the present invention have a hydroxyl value of 5. It is uniformly dispersed because it is 0.0 mgKOH / g or more and 30 mgKOH / g or less.

[Optical film]
The optical film of the present invention is an optical film in which a coating film containing the polymer particles of the present invention and a binder is formed on a base film, and the polymer particles are dispersed in the binder as a dispersoid. It is what has been. The optical film of the present invention can be obtained by applying the dispersion of the present invention on a substrate film. The optical film of the present invention is obtained by coating (coating) the dispersion liquid of the present invention on a base film and drying it (by distilling off volatile components such as an organic solvent contained in the dispersion liquid). It can manufacture by the method of forming a coating film on a film.

The base film is preferably transparent. Examples of the transparent base film include polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose (TAC), polycarbonate polymers, and polymethyl methacrylate. And a film using a polymer such as a (meth) acrylic polymer. In addition, as a transparent substrate film, polystyrene, styrene polymer such as acrylonitrile / styrene copolymer, polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, olefin polymer such as ethylene / propylene copolymer, chloride A film using a polymer such as a vinyl polymer or an amide polymer such as nylon or aromatic polyamide is also included. Further, as a transparent base film, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenyl sulfide polymer, vinyl alcohol polymer, vinylidene chloride Examples thereof include films using polymers such as polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, and blends of these polymers. As the substrate film, a film having a particularly low birefringence is preferably used. In addition, a film in which an easy-adhesion layer such as (meth) acrylic resin, copolymerized polyester resin, polyurethane resin, styrene-maleic acid grafted polyester resin, acrylic grafted polyester resin or the like is further provided on these films is also used as the base film. Can be used.

The thickness of the base film can be determined as appropriate, but is generally in the range of 10 to 500 μm and in the range of 20 to 300 μm from the viewpoint of strength, workability such as handling, and thin layer properties. It is preferable that it is within a range of 30 to 200 μm. Moreover, you may add additives, such as a ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index regulator, and an enhancer, to the said base film.

The coating method of the dispersion of the present invention on a base film includes bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, and air coating. Known coating methods such as knife coating and dipping method may be mentioned.

〔paint〕
The polymer particles of the present invention can also be used in paints and can be contained in paints as coating film softeners, paint matting agents, light diffusing agents, and the like. The coating material of the present invention contains the polymer particles of the present invention. When the paint of the present invention contains a hydrophilic solvent such as an alcohol solvent, the polymer particles can be uniformly dispersed.

前記 The paint contains a binder resin as necessary. As the binder resin, a resin soluble in an organic solvent or water, or an emulsion-type aqueous resin that can be dispersed in water can be used, and any known binder resin can be used. As the binder resin, for example, trade names “Dianar (registered trademark) LR-102” and “Dianar (registered trademark) BR-106” manufactured by Mitsubishi Rayon Co., Ltd., or products manufactured by Dainichi Seika Kogyo Co., Ltd. Acrylic resin such as “medium VM”; alkyd resin; polyester resin; polyurethane resin such as “E-5221P” manufactured by Daido Kasei Kogyo Co., Ltd .; chlorinated polyolefin resin; amorphous polyolefin resin; It is done. These binder resins can be appropriately selected depending on the adhesion of the paint to the substrate to be coated, the environment in which it is used, and the like.

The blending amount of the polymer particles is appropriately adjusted depending on the thickness of the coating film formed from the coating material containing the binder resin, the average particle diameter of the polymer particles, the coating method, the application to be used, etc., but 100 parts by weight of the binder resin On the other hand, it is preferably in the range of 1 to 300 parts by weight, and more preferably in the range of 5 to 100 parts by weight. When the blending amount of the polymer particles is less than 1 part by weight with respect to 100 parts by weight of the binder resin, the matte effect may not be sufficiently obtained. In addition, when the blending amount of the polymer particles exceeds 300 parts by weight with respect to 100 parts by weight of the binder resin, the viscosity of the coating becomes too high, and the dispersion of the polymer particles may occur. In some cases, the appearance of the coating film surface may be deteriorated, such as micro cracks occurring on the coating film surface obtained by coating the coating material, or roughness of the coating film surface obtained.

The paint contains a medium as required. As the medium, it is preferable to use a solvent (solvent) capable of dissolving the binder resin or a dispersion medium capable of dispersing the binder resin. As the dispersion medium or solvent, any of an aqueous medium and an oily medium can be used. Oil-based media include hydrocarbon solvents such as toluene, xylene and cyclohexane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane, ethylene glycol diethyl ether and ethylene glycol mono And ether solvents such as butyl ether. Examples of the aqueous medium include water and alcohols (for example, isopropanol). These media may use only 1 type and may mix and use 2 or more types. The content of the medium in the coating is usually in the range of 20 to 60% by weight with respect to the total amount of the coating.

In addition, paints include curing agents, colorants (external pigments, color pigments, metal pigments, mica powder pigments, dyes, etc.), antistatic agents, leveling agents, fluidity modifiers, ultraviolet absorbers, light stabilizers, etc. Other additives may be included.

The substrate to be coated with the paint is not particularly limited, and a substrate according to the application can be used.
For example, in an optical application, a glass substrate, a transparent substrate made of a transparent substrate resin, or the like is used as a substrate to be coated. A transparent substrate is used as the substrate to be coated, and a coating material that does not contain a colorant (a coating agent for light diffusion) is applied onto the transparent substrate to form a transparent coating film. An optical film such as a glare film can be produced. In this case, the polymer particles function as a light diffusing agent.

Further, matte paper can be produced by using paper as a substrate to be coated and applying a paint (paper coating agent) containing no colorant to form a transparent coating film.

The coating method of the paint is not particularly limited, and any known method can be used. Examples of the coating method include a comma direct method, a spin coating method, a spray coating method, a roll coating method, a dipping method, a knife coating method, a curtain flow method, and a laminating method. The paint may be diluted by adding a diluent to adjust the viscosity as necessary. Diluents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; water An alcohol solvent or the like. These diluents may be used alone or in combination of two or more. When manufacturing an optical film, it is preferable to use a method in which irregularities derived from polymer particles are formed on the surface of the coating film as a coating method.

[Molding materials and optical members]
The polymer particles of the present invention include a molding material formed by mixing the polymer particles with a transparent resin (binder), and a light diffuser formed by molding the molding material (for example, an illumination cover such as an LED lighting cover). It can also be used for optical members. When the polymer particles of the present invention are used in an optical member such as the light diffuser, the polymer particles are mixed with a transparent resin (binder) made of a polymer having a polar group (for example, PET). Familiar with the binder.

The molding material of the present invention contains the polymer particles of the present invention and a transparent resin. The transparent resin is a base material of the molding material. For example, (meth) acrylic resin, polycarbonate resin, polystyrene resin, (meth) acrylic-styrene resin ((meth) acrylic) acid ester and styrene And the like). Among them, polystyrene resin or (meth) acryl-styrene resin is preferable as the transparent resin.

The amount of the polymer particles contained in the molding material is preferably in the range of 0.01 to 5 parts by weight, and in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the transparent resin. It is more preferable. Additives such as ultraviolet absorbers, antioxidants, heat stabilizers, light stabilizers, and fluorescent brighteners may be added to the molding material.

The molding material can be obtained by melt-kneading the transparent resin and the polymer particles with a single screw extruder or a twin screw extruder. The molding material may be a pellet-shaped molding material (master pellet) obtained by pelletizing a molding material obtained by melt kneading.

The optical member of the present invention is formed by molding the molding material of the present invention, that is, a molded body of the molding material of the present invention. In the optical member, the polymer particles function as a light diffusing agent. Therefore, the optical member functions as a light diffuser such as a light diffusion plate and can be used as an LED illumination cover or the like.

The thickness and shape of the optical member can be appropriately selected depending on the use of the optical member.

As a method for obtaining an optical member by molding a molding material, for example, a method of molding a molding material obtained by melt kneading into a plate shape or the like via a T die and a roll unit, a pellet-shaped molding material (master pellet) The method etc. which shape | mold a sheet | seat by injection molding, press molding, etc. can be used.

[Other uses]
The polymer particles of the present invention can also be used for products other than optical films, such as inks and external preparations (cosmetics, etc.). In addition, when the polymer particles of the present invention are used for an ink or an external preparation, the polymer particles can be uniformly dispersed when the ink or the external preparation contains a hydrophilic solvent such as an alcohol solvent.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. First, in the following examples and comparative examples, the volume average particle diameter of the polymer particles and the measurement method of the coefficient of variation of the particle diameter, the measurement method of the volume average particle diameter of the seed particles used for the production of the polymer particles, the polymer The method for measuring the hydroxyl value of the particles and the alcohol solvent dispersion test will be described.

[Measurement method of volume average particle diameter of polymer particles and coefficient of variation of particle diameter]
The volume average particle diameter of the polymer particles is measured by Coulter Multisizer III (Beckman Coulter, Inc. measurement device). Measurement shall be performed using an aperture calibrated according to the Multisizer ™ 3 User's Manual issued by Beckman Coulter, Inc.

In addition, the aperture used for the measurement is appropriately selected according to the size of the particle to be measured. When an aperture having a size of 50 μm was selected, the current (aperture current) was set to −800 and the gain (gain) was set to 4.

As a sample for measurement, 0.1 g of polymer particles in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution was mixed with a touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) and an ultrasonic cleaner (stock) Dispersed using “ULTRASONIC CLEANER VS-150” manufactured by Vervo Crear, Inc., and used as a dispersion. During the measurement, the beaker is gently stirred to the extent that bubbles do not enter, and the measurement is terminated when 100,000 polymer particles are measured. The volume average particle diameter of the polymer particles is an arithmetic average in a volume-based particle size distribution of 100,000 particles.

The variation coefficient (CV value) of the particle diameter of the polymer particles is calculated by the following mathematical formula.
Coefficient of variation of particle diameter of polymer particles = (standard deviation of volume distribution of polymer particles based on volume / volume average particle diameter of polymer particles) × 100

[Measurement method of volume average particle diameter of seed particles used for production of polymer particles]
The volume average particle size of the seed particles used for the production of the polymer particles is measured by a laser diffraction / scattering particle size distribution measuring device (“LS 13 320” manufactured by Beckman Coulter, Inc.) and a universal liquid sample module.

Specifically, 0.1 g of the seed particle dispersion in 10 ml of a 0.1 wt% nonionic surfactant aqueous solution, touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) and ultrasonic cleaner (stock) Dispersed using “ULTRASONIC CLEANER VS-150” manufactured by Vervo Crear, Inc., and used as a dispersion.

The measurement is performed in a state where the seed particles are dispersed by performing pump circulation in the universal liquid sample module, and in a state where the ultrasonic unit (ULM ULTRASONIC MODULE) is activated, and the volume average particle diameter of the seed particles ( Calculate the arithmetic mean diameter in the volume-based particle size distribution. The measurement conditions are shown below.
Medium = Water Refractive index of medium = 1.333
Refractive index of solid = refractive index of seed particles (when seed particles are polymethyl methacrylate particles, 1.495)
PIDS relative concentration: about 40-55%

[Method for measuring hydroxyl value of polymer particles]
The hydroxyl value of the polymer particles is measured according to a hydroxyl value quantitative analysis method (JIS K 0070-1992). Specifically, the hydroxyl value of the polymer particles is measured according to the following procedure.

<Method for measuring acid value for measuring hydroxyl value (JIS K 0070)>
2 g of a sample and 20 mL of pyridine solvent were put into a 200 mL flat bottom flask and dispersed while stirring at room temperature for 1 hour. Then, 3 drops of a phenolphthalein reagent were added and titrated with a 0.5 mol / L potassium hydroxide ethanol solution. The point where the color changes to magenta is the end point. A blank test is also performed by the same method, and the acid value is calculated from the following formula. The measurement is performed twice, and the average value is taken as the acid value.

<Acid value calculation formula>
Acid value (mgKOH / g) = (V1-V0) × f × 0.1 × 56.11 ÷ S
Where S: mass of sample collected (g)
V0: Amount of 0.1 mol / L potassium hydroxide ethanol solution required for the blank test (mL) ... Blank titration (mL)
V1: Amount of 0.1 mol / L potassium hydroxide ethanol solution required for this test (mL) ... Sample titration (mL)
f: Factor of 0.1 mol / L potassium hydroxide ethanol solution: 1.0

<Analytical procedure>
Add 2 g of the sample and 3 mL of the acetylating agent to a 200 mL flat bottom flask, and mix by stirring. Add 20 mL of the pyridine solution, stir for 10 minutes, and then react in an oil bath at 110 ° C. for 1 hour. Thereafter, the mixture is stirred for 10 minutes with a shaker, allowed to cool, added with 1 mL of distilled water, and reacted in an oil bath at 105 ° C. for 10 minutes. Then, 3 drops of phenolphthalein reagent are added, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution, and the point at which the color changes to reddish purple is taken as the end point. In addition, a blank test is performed by the same method, and the hydroxyl value is calculated by the following formula. The measurement is performed twice, and the average value is the hydroxyl value.

<Hydroxyl value calculation formula>
Hydroxyl value (mgKOH / g)
= [(V0−V1) × f × 0.5 × 56.11 ÷ S] + acid value where
S: Weight of collected sample (g)
V0: Amount of 0.5 mol / L potassium hydroxide ethanol solution required for the blank test (mL) ... Blank titration (mL)
V1: Amount of 0.5 mol / L potassium hydroxide ethanol solution required for this test (mL) ... Sample titration (mL)
f: Factor of 0.5 mol / L potassium hydroxide ethanol solution: 1.0

[Alcohol solvent dispersion test]
In the alcohol-based solvent dispersion test, 0.1 g of particles and 5 g of methanol or isopropyl alcohol as an alcohol-based solvent were weighed in a 10 mL capacity plastic ointment jar, and stirred and defoamed (Awatori Nertaro (registered trademark) AR-). 100: manufactured by Shinky Corporation) for 3 minutes. After stirring, drop 1 drop of the dispersion liquid onto a glass plate with a dropper, and cover the glass from above. Then, an evaluation test is performed by observing the dispersion state with a digital microscope VHX (manufactured by Keyence Corporation). From the observation results, it is determined that “◎” indicates a case where it is dispersed in both methanol and isopropyl alcohol, “◯” indicates a case where it is dispersed in either one, and “×” indicates a case where it is not dispersed in either.

[Production Example 1 of Seed Particles]
In a separable flask equipped with a stirrer, a thermometer, and a reflux condenser, 3000 g of water as an aqueous medium, 500 g of methyl methacrylate as a monofunctional (meth) acrylic monomer, and n-octyl as a molecular weight regulator Mercaptan (5 g) was charged, the inside of the separable flask was purged with nitrogen while stirring the contents of the separable flask, and the internal temperature of the separable flask was raised to 70 ° C. Furthermore, while maintaining the internal temperature of the separable flask at 70 ° C., 2.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask, followed by polymerization reaction for 12 hours to obtain an emulsion (seed particle dispersion). )

The obtained emulsion contains 14% by weight of solid content (polymethyl methacrylate particles), and the solid content is a spherical particle (seed) having a volume average particle diameter of 0.45 μm and a weight average molecular weight of 15000. Particles).

[Production Example 2 of Seed Particles]
In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 600 g of water as an aqueous medium, 70 g of the emulsion obtained in Production Example 1 of seed particles, and methacryl as a monofunctional (meth) acrylic monomer 100 g of methyl acid and 1.0 g of n-octyl mercaptan as a molecular weight modifier were charged, and the contents of the separable flask were stirred with a stirrer to replace the space in the separable flask with nitrogen, and the inner temperature of the separable flask The temperature was raised to 70 ° C. Furthermore, after adding 0.5 g of potassium persulfate as a polymerization initiator while maintaining the internal temperature of the separable flask at 70 ° C., the polymerization reaction was performed over 8 hours while maintaining the internal temperature of the separable flask at 70 ° C. The emulsion (seed particle dispersion) was obtained.

The obtained emulsion contained 14% by weight of solid content (polymethyl methacrylate particles), and the solid content was true spherical particles (seed particles) having a volume average particle diameter of 1.00 μm. The emulsion containing the spherical particles was used as a seed particle dispersion in Examples and Comparative Examples of polymer particles described later.

[Example 1: Production example of polymer particles by seed polymerization]
In a 5 L reactor equipped with a stirrer and a thermometer, 600 g of styrene as a monofunctional styrene monomer, 50 g of methyl methacrylate as a monofunctional (meth) acrylic monomer, and a crosslinkable monomer And 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Kasei Co., Ltd .; represented by the general formula (1)) as a hydroxyl group-containing monomer represented by the general formula (1) 50 g in which R ¹ is a hydrogen atom, R ² is a cyclohexanediyl group, R ³ is a divalent group represented by the formula (2), and m = 1 and n = 1. Then, 8 g of 2,2′-azobisisobutyronitrile as a polymerization initiator was dissolved in each other to obtain a monomer mixture.

The obtained monomer mixture was mixed with 1000 g of a surfactant aqueous solution obtained by dissolving 10 g of polyoxyethylene octylphenyl ether as a nonionic surfactant in 990 g of ion-exchanged water in advance, and high-speed emulsification / dispersion It was put into a machine (trade name “Homomixer MARK II 2.5 type”, manufactured by Primix Co., Ltd.) and treated at a rotational speed of 10,000 rpm for 10 minutes to obtain an emulsion. To this emulsion, 143 g of seed particle dispersion (20 g of solid content (polymethyl methacrylate)) having a volume average particle diameter of 1.00 μm obtained in Production Example 2 of the seed particles is added, and stirred at 30 ° C. for 3 hours. To obtain a dispersion.

To this dispersion, 2000 g of a 4% by weight aqueous solution of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSENOL (registered trademark) GH-17”) as a polymer dispersion stabilizer and a polymerization inhibitor 0.6 g of sodium nitrate was added, and then the polymerization reaction was carried out by stirring at 70 ° C. for 5 hours and then stirring at 105 ° C. for 2.5 hours. The dispersion after polymerization was dehydrated with a pressure filter, washed with warm water, and then vacuum-dried at 70 ° C. for 24 hours to obtain polymer particles composed of a crosslinked (meth) acryl-styrene copolymer resin ( Hereinafter, referred to as “polymer particle A”).

The resulting polymer particles A had a volume average particle size of 3.8 μm, a particle size variation coefficient of 11.3%, and a hydroxyl value of 12.3 mgKOH / g. In this example, the amount of the hydroxyl group-containing monomer represented by the general formula (1) is 3.1 mol% with respect to the total amount of the vinyl monomer for seed polymerization used in this example. The content of the structural unit derived from the hydroxyl group-containing monomer represented by the general formula (1) in the polymer particle A is 3.1 mol% (4.9 wt%). It is.

[Example 2: Production example of polymer particles by seed polymerization]
Without using methyl methacrylate, the amount of styrene used was changed to 400 g, the amount of ethylene glycol dimethacrylate was changed to 400 g, and 1,4 as the hydroxyl group-containing monomer represented by the general formula (1) -Instead of 50 g of cyclohexanedimethanol monoacrylate, 3-hydroxy-1-adamantyl acrylate (Mitsubishi Gas Chemical Co., Ltd .; a compound represented by the above general formula (1), wherein R ¹ is a hydrogen atom, R ² is A polymer in the same manner as in Example 1 except that 200 g of an adamantanediyl group, R ³ is a divalent group represented by the formula (2) and m = 0 and n = 0) was used. Particles (hereinafter referred to as “polymer particles B”) were obtained.

The resulting polymer particles B had a volume average particle size of 3.7 μm, a particle size variation coefficient of 12.4%, and a hydroxyl value of 23.2 mgKOH / g. In this example, the amount of the hydroxyl group-containing monomer represented by the general formula (1) was 13.3 mol% with respect to the total amount of the vinyl monomer for seed polymerization used in this example. The content of the structural unit derived from the hydroxyl group-containing monomer represented by the general formula (1) in the polymer particle B is 12.9 mol% (19.6 wt%). It is.

[Example 3: Production of polymer particles by seed polymerization]
Without using methyl methacrylate, the amount of styrene used was changed to 550 g, the amount of ethylene glycol dimethacrylate was changed to 400 g, and 1,4 as the hydroxyl group-containing monomer represented by the general formula (1) -Instead of 50 g of cyclohexanedimethanol monoacrylate, 3-hydroxy-1-adamantyl methacrylate (Mitsubishi Gas Chemical Co., Ltd .; a compound represented by the above general formula (1), wherein R ¹ is a methyl group and R ² is A polymer similar to that of Example 1 except that 50 g of an adamantanediyl group, R ³ is a divalent group represented by the formula (2), and m = 0 and n = 0 is used. Particles (hereinafter referred to as “polymer particles C”) were obtained.

The resulting polymer particles C had a volume average particle size of 3.7 μm, a particle size variation coefficient of 10.7%, and a hydroxyl value of 5.26 mgKOH / g. Further, in this example, the amount of the hydroxyl group-containing monomer represented by the general formula (1) is 2.8 mol% with respect to the total amount of the vinyl monomer for seed polymerization used in this example. The content of the structural unit derived from the hydroxyl group-containing monomer represented by the general formula (1) in the polymer particle B is 2.7 mol% (4.9 wt%). It is.

[Comparative Example 1: Production Example of Polymer Particles]
300 g of styrene as a monofunctional styrene monomer, 400 g of ethylene glycol dimethacrylate as a crosslinkable monomer, and 1,4-cyclohexanedi as a hydroxyl group-containing monomer represented by the general formula (1) Polymer particles (hereinafter referred to as “polymer particles D”) were obtained in the same manner as in Example 1, except that 300 g of methanol monoacrylate was used.

The resulting polymer particles D had a volume average particle size of 3.8 μm, a particle size variation coefficient of 12.3%, and a hydroxyl value of 64.1 mgKOH / g. Moreover, in this comparative example, the usage-amount of the hydroxyl-containing monomer represented by General formula (1) is 23.6 mol% with respect to the total amount of the vinyl monomer for seed polymerization used in the present Example. Therefore, the content of the structural unit derived from the hydroxyl group-containing monomer represented by the general formula (1) in the polymer particle B is 22.9 mol% (29.4 wt%). %).

[Comparative Example 2: Production Example of Polymer Particles]
Example 1 except that 100 g of methyl methacrylate as a monofunctional (meth) acrylic monomer, 600 g of styrene as a monofunctional styrene monomer, and 300 g of ethylene glycol dimethacrylate as a crosslinkable monomer were used. In the same manner, polymer particles (hereinafter referred to as “polymer particles E”) were obtained. The resulting polymer particles E had a volume average particle size of 3.7 μm, a particle size variation coefficient of 11.9%, and a hydroxyl value of 2.42 mgKOH / g.

[Preparation of antiglare film dispersion and production of antiglare film]
Using the polymer particles A to E produced in Examples 1 to 3, Comparative Example 1 and Comparative Example 2, respectively, production of five types of antiglare films was attempted.
That is, first, 80 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name “Aronix (registered trademark) M-305”, manufactured by Toagosei Co., Ltd.) as an ultraviolet curable resin, and an organic solvent 120 parts by weight of a mixed solution of isopropanol (IPA) and cyclopentanone (volume ratio of IPA to cyclopentanone = 5: 5) and manufactured in Examples 1 to 3, Comparative Example 1 and Comparative Example 2 above. 5 parts by weight of the polymer particles A to E and a photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, trade name “Irgacure (registered trademark) 907” And 5 parts by weight of BASF (registered trademark) Japan Co., Ltd.) to prepare five types of antiglare film dispersions as dispersions. It was.

A polyethylene terephthalate (PET) film having a thickness of 0.2 mm, which is a transparent plastic film, was prepared as a base film. A coating film was formed by applying the antiglare film dispersion on one side of the polyethylene terephthalate film using a bar coater having a wet film thickness of 60 μm. However, the antiglare film dispersion containing the polymer particles E produced in Comparative Example 2 was insufficient in dispersibility and could not be applied.

Next, the said coating film was dried by heating at 80 degreeC for 1 minute (s). Thereafter, the coating film was cured by irradiating the coating film with ultraviolet light with an integrated light quantity of 300 mJ / cm ^{2 using} a high-pressure mercury lamp, thereby forming an antiglare hard coat layer. As a result, four types of antiglare hard coat films respectively containing the polymer particles A to D produced in Examples 1 to 3 and Comparative Example 1 were prepared as antiglare films (molded articles). .

[Example 4: Production of polymer particles by seed polymerization]
Instead of 50 g of 1,4-cyclohexanedimethanol monoacrylate as a hydroxyl group-containing monomer represented by the general formula (1), cyclohexanedimethanol monovinyl ether (manufactured by Nippon Carbide Industries Co., Ltd .; represented by the general formula (1) Compound in which R ¹ is a hydrogen atom, R ² is a cyclohexanediyl group, R ³ is a divalent group represented by the formula (3), and m = 1 and n = 1) 50 g Polymer particles (hereinafter referred to as “polymer particles F”) were obtained in the same manner as in Example 1 except that was used.

The resulting polymer particles F had a volume average particle size of 3.9 μm, a particle size variation coefficient of 11.4%, and a hydroxyl value of 13.2 mgKOH / g. In this example, the amount of the hydroxyl group-containing monomer represented by the general formula (1) is 3.6 mol% with respect to the total amount of the vinyl monomer for seed polymerization used in this example. The content of the structural unit derived from the hydroxyl group-containing monomer represented by the general formula (1) in the polymer particle F is 3.1 mol% (4.9 wt%). It is.

[Example 5: Production example of polymer particles by suspension polymerization]
600 g of butyl methacrylate as a monofunctional (meth) acrylic monomer, 300 g of ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) as a crosslinkable monomer, and a hydroxyl group represented by the general formula (1) 1,4-cyclohexanedimethanol monoacrylate (Nippon Kasei Co., Ltd .; a compound represented by the above general formula (1), wherein R ¹ is a hydrogen atom, R ² is a cyclohexanediyl group, 4. R ³ is a divalent group represented by the formula (2), m = 1, n = 1, and 100 g of 2,2′-azobisisobutyronitrile as a polymerization initiator. An oil phase was prepared by mixing 0 g and 2.0 g of benzoyl peroxide. Further, 2500 g of deionized water as an aqueous medium and 30.1 g of magnesium pyrophosphate produced by the metathesis method as a dispersant were mixed to prepare an aqueous phase.

Next, the oil phase was dispersed in the aqueous phase to obtain a dispersion. A suspension was prepared by stirring at a rotational speed of 2000 rpm using a stirrer (trade name “Homomixer MARK II 2.5 type”, manufactured by Primix Co., Ltd.). Thereafter, this suspension was put into a polymerization vessel having an internal volume of 5 L equipped with a stirrer and a thermometer, the internal temperature of the polymerization vessel was raised to 55 ° C., and stirring of the suspension was continued for 6 hours. Went. Hydrochloric acid was added to the resulting suspension until the pH became 2 or lower to decompose magnesium pyrophosphate, the aqueous phase was removed by filtration, washed, and then dried in vacuo at 70 ° C. for 24 hours to polymer particles ( (Hereinafter referred to as “polymer particle G”).

The resulting polymer particles G had a volume average particle size of 15.9 μm, a particle size variation coefficient of 32.4%, and a hydroxyl value of 17.2 mgKOH / g. In this example, the content of the structural unit derived from the hydroxyl group-containing monomer represented by the general formula (1) in the polymer particle G is 8.1 mol% (10.0 wt%).

[Evaluation method of antiglare property of antiglare film]
The method for evaluating the antiglare property of the antiglare film produced by the above method will be described. A surface of each of the produced antiglare films, which is not the coated surface, is attached to an ABS resin (acrylonitrile-butadiene-styrene copolymer resin) plate, and a fluorescent lamp with a luminance of 10000 cd / cm ² is placed from a location 2 m away from the antiglare film. The antiglare film was visually evaluated on the coated surface and visually evaluated. The evaluation criteria for anti-glare are anti-glare when the outline of the reflected image of the fluorescent lamp is not clearly visible (“Good”), and when the outline of the reflected image of the fluorescent lamp is clearly visible, anti-glare Evaluated as “x” (bad).

For Examples 1 to 5, Comparative Example 1 and Comparative Example 2, the volume average particle diameter (μm) of the seed particles used for the production of the polymer particles, the vinyl monomer for seed polymerization [methyl methacrylate (MMA) ), Styrene (St), ethylene glycol dimethacrylate (EGDMA), 1,4-cyclohexanedimethanol monoacrylate (CHDMMA), 3-hydroxy-1-adamantyl acrylate (HADA), 3-hydroxy-1-adamantyl methacrylate (HADM) ) And cyclohexanedimethanol monoacrylate (CHMVE)], and the content of the structural unit (hydroxyl group-containing monomer structural unit) derived from the hydroxyl group-containing monomer represented by the general formula (1) (% By weight), volume average particle diameter (μm) of polymer particles, and coefficient of variation of particle diameter (CV value) ) (%) Measurement results, measurement value of hydroxyl value of polymer particles (mgKOH / g), evaluation result of alcohol solvent dispersion test of polymer particles, and dispersion containing polymer particles applied to base film Table 1 shows the evaluation results of the antiglare property of the antiglare film formed by processing.

From the results shown in Table 1, when the hydroxyl value of the polymer particles is 5.0 mgKOH / g or more and 30 mgKOH / g or less, the evaluation result of the alcohol solvent dispersion test and the evaluation result of the antiglare property of the antiglare film are Both were found to give good results.

On the other hand, when the hydroxyl value of the polymer particles deviated from the above range, either the evaluation result of the alcohol solvent dispersion test or the evaluation result of the antiglare property of the antiglare film resulted in a failure. That is, the polymer particle E having a hydroxyl value of less than 5.0 mgKOH / g has a poor evaluation result of the alcohol dispersion test, and the coating cannot be performed, so that the antiglare film cannot be evaluated for antiglare properties. . Moreover, the polymer particle D with a hydroxyl value larger than 30 mgKOH / g had a poor antiglare evaluation result of the antiglare film. This is because, when the hydroxyl value of the polymer particles is too large, the polymer particles are aggregated due to insufficient aggregation of the polymer particles in the process of volatilizing the solvent after coating the dispersion on the base film. This is considered to be because the projections that provide antiglare properties could not be sufficiently formed.

[Preparation example of paint]
7 parts by weight of the polymer particles G obtained in Example 5 and 50 parts by weight of an acrylic binder resin (trade name “Dyanal (registered trademark) LR-102” manufactured by Mitsubishi Rayon Co., Ltd.) as a binder resin; , 100 parts by weight of toluene as a medium and 20 parts by weight of methyl ethyl ketone, and 15 parts by weight of an isocyanate-based curing agent (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate (registered trademark) TKA-100”) as a curing agent Using a defoamer, the coating was obtained by mixing for 3 minutes and defoaming for 1 minute.

The obtained paint was applied on an ABS resin (acrylonitrile-butadiene-styrene resin) plate using a coating apparatus in which a blade having a clearance of 50 μm was set, and then dried to obtain a coating film. When the gloss (60 °) of the obtained coating film was measured using a gloss checker (model number: IG-330) manufactured by Horiba, Ltd., the gloss (60 °) was 11.

The polymer particles of the present invention include, for example, a light diffusing agent for optical members (optical films such as light diffusing films and antiglare films, light diffusing bodies formed by mixing polymer particles with a binder, etc.), It can be used as an additive for paint, an additive for ink, an additive for external preparations such as cosmetics, and the like.

The present invention can be implemented in various other forms without departing from the spirit or main features thereof. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

In addition, this application claims priority based on Japanese Patent Application No. 2015-072817 filed in Japan on March 31, 2015. By this reference, the entire contents thereof are incorporated into the present application.

Claims

At least one of a structural unit derived from a monofunctional (meth) acrylic monomer and a structural unit derived from a monofunctional styrene monomer;
The following general formula (1)

(In the above formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a divalent cyclic hydrocarbon group which may have a substituent, and m and n are each independently 0-4. R 3 represents the following formulas (2) to (4):

In the above formulas (2) to (4)

Represents the binding position)
A structural unit derived from a hydroxyl group-containing monomer represented by:
Including a structural unit derived from a crosslinkable monomer,
A polymer particle having a hydroxyl value of 5.0 mgKOH / g or more and 30 mgKOH / g or less.
The polymer particles according to claim 1,
R 3 is a divalent group represented by the formula (2).
The polymer particles according to claim 1 or 2,
A polymer particle comprising a structural unit derived from the hydroxyl group-containing monomer in a range of 2 mol% or more and less than 20 mol%.
The polymer particles according to any one of claims 1 to 3,
A polymer particle comprising 3 to 50% by weight of a structural unit derived from the crosslinkable monomer.
The polymer particles according to any one of claims 1 to 4,
Polymer particles having a particle diameter variation coefficient of 15% or less.
The polymer particles according to any one of claims 1 to 5,
The polymer particle, wherein the monofunctional (meth) acrylic monomer contains a monofunctional (meth) acrylic monomer having a solubility in water of 25 ° C. of 2.00% by weight or less.
A method for producing polymer particles in which a vinyl monomer is polymerized to produce polymer particles,
The vinyl monomer is at least one of a monofunctional (meth) acrylic monomer and a monofunctional styrene monomer,
The following general formula (1)

(In the above formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a divalent cyclic hydrocarbon group which may have a substituent, and m and n are each independently 0-4. R 3 represents the following formulas (2) to (4):

In the above formulas (2) to (4)

Represents the binding position)
A hydroxyl group-containing monomer represented by:
Including a crosslinkable monomer,
The method for producing polymer particles, wherein the vinyl monomer contains the hydroxyl group-containing monomer in a range of 2 mol% or more and less than 20 mol%.
It is a manufacturing method of the polymer particle according to claim 7,
R 3 is a divalent group represented by the formula (2). A method for producing polymer particles.
A method for producing polymer particles according to claim 7 or 8,
The method for producing polymer particles, wherein the polymerization of the vinyl monomer is seed polymerization performed by absorbing the vinyl monomer in a seed particle in an aqueous medium.
A method for producing polymer particles according to claim 9,
The seed particle includes at least one of a structural unit derived from a monofunctional (meth) acrylic monomer and a structural unit derived from a monofunctional styrenic monomer. .
A method for producing polymer particles according to any one of claims 7 to 10,
The method for producing polymer particles, wherein the polymer particles have a hydroxyl value of 5.0 mgKOH / g or more and 30 mgKOH / g or less.
The polymer particles according to any one of claims 1 to 6 and a binder,
A dispersion liquid, wherein the polymer particles are dispersed in the binder as a dispersoid.
An optical film in which a coating film comprising the polymer particles according to any one of claims 1 to 6 and a binder is formed on a base film,
An optical film, wherein the polymer particles are dispersed in the binder as a dispersoid.
A paint comprising the polymer particles according to any one of claims 1 to 6.
A molding material comprising the polymer particles according to any one of claims 1 to 6 and a transparent resin.
An optical member, which is a molded body of the molding material according to claim 15.