KR20220069838A - Low-reflection coating agent, coating agent kit, cured product and laminate - Google Patents

Abstract

Provided are: a low-reflection coating agent; a coating agent kit; a cured article; and a laminate article. The present disclosure provides a low-reflection coating agent comprising: an acidic group-containing polymethacrylate; hollow inorganic particles; and solid alumina particles, wherein the content of the solid alumina particles is 2-15 wt% on a dry solid basis. The present disclosure also provides a coating agent kit comprising: a low-reflective coating agent containing 2-15 wt% of solid alumina particles on a dry solid basis; and an anchor agent containing solid alumina particles.

Description

Low-reflection coatings, coating kits, cured products and laminates {LOW-REFLECTION COATING AGENT, COATING AGENT KIT, CURED PRODUCT AND LAMINATE}

[0001]

The present disclosure relates to low-reflection coatings, coating kits, cured products and laminates.

[0002]

DESCRIPTION OF RELATED ART In recent years, liquid crystal display devices are used as display apparatuses, such as a TV and a personal computer. In such a liquid crystal display device, it is proposed to use an antireflection film including a low refractive index layer in order to prevent reflection of external light and improve image quality (Patent Document 1).

[0003] [Patent Document 1] Japanese Patent Laid-Open No. 2014-085383

[0004]

Hollow particles may be used to give the coating agent low reflection (low refractive index). In this case, since the particles are hollow, there is a problem that scratch resistance is lowered.

[0005]

By further mix|blending a solid alumina particle with respect to the coating agent which mix|blended the hollow particle, the fall of abrasion resistance can be suppressed. However, it was found that stability was a problem when the hollow particles and solid alumina particles coexist in one system.

[0006]

Therefore, one of the problems to be solved by the invention is to provide a low-reflection coating agent having good stability.

[0007]

One of the problems to be solved by the present invention is to provide a coating agent kit capable of producing a laminate having good scratch resistance while maintaining low reflectivity.

[0008]

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solved by using a specific component, as a result of earnestly examining.

[0009]

According to the present disclosure, the following items are provided.

(Item 1)

acidic group-containing poly (meth) acrylate;

hollow inorganic particles and

comprising solid alumina particles;

The content of the solid alumina particles is 2 to 15 mass% of the solid content

Anti-reflective coatings.

(Item 2)

The low-reflection coating agent according to the above item comprising a (meth)acryloyl group-containing perfluoropolyether.

(Item 3)

A low-reflection coating agent containing 2 to 15 mass % of solid alumina particles in solid content, and

A coating kit comprising an anchor agent comprising solid alumina particles.

(Item 4)

A cured product of the low-reflection coating agent according to any one of the above items and/or the coating agent kit according to the above items.

(Item 5)

A laminate comprising the cured product according to the above item.

[0010]

In the present disclosure, the one or more features may be provided in further combination in addition to the specified combination.

[0011]

The low-reflection coating agent according to the present embodiment has good stability.

[0012]

By using the coating agent kit according to the present embodiment, a laminate having good low reflectivity and good scratch resistance can be manufactured.

[0013]

Throughout the present disclosure, numerical ranges of each physical property value, content, etc. may be appropriately set (eg, by selecting from the upper and lower limits described in each item below). Specifically, when A3, A2, A1 (referred to as A3 > A2 > A1), etc., are exemplified as the upper and lower limits of the numerical value α for the numerical value α, the range of the numerical value α is A3 or less, A2 or less, less than A3, less than A2, A1 or more A2 or more, greater than A1, greater than A2, A1 to A2 (A1 to A2 or less), A1 to A3, A2 to A3, A1 to less than A3, A1 or more and less than A2, A2 or more A3 or less, greater than A1 and A3 Less than, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than or equal to A3, greater than A1 and less than or equal to A2, greater than A2 and less than or equal to A3 are exemplified.

[0014]

[Low reflection coating agent: also called coating agent]

The present disclosure is an acid group-containing poly (meth) acrylate,

hollow inorganic particles and

comprising solid alumina particles;

The content of the solid alumina particles is 2 to 15 mass% of the solid content

A low-reflection coating is provided.

[0015]

<Poly (meth)acrylate containing an acid group>

The acidic group-containing poly(meth)acrylate may be used alone or in combination of two or more.

[0016]

In the present disclosure, “acidic group-containing poly(meth)acrylate” refers to a compound having one or more acidic groups and two or more (meth)acryloyl groups.

[0017]

In the present disclosure, "acidic group" means a group in which one or more hydrogen atoms are dissociated to generate a base.

[0018]

As an acidic group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are illustrated.

[0019]

In the present disclosure, "(meth)acryl" means "at least one selected from the group consisting of acryl and methacryl". Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". In addition, "(meth)acryl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

[0020]

It is thought that stability of a low reflective coating agent can be improved by using acidic-group containing poly(meth)acrylate. This is considered to be because the acidic group-containing poly(meth)acrylate acts as a dispersing agent for the solid alumina particles and prevents aggregation and precipitation of the solid alumina particles. In addition, the above is only one hypothesis, and it is not intended that this invention is limited by the said hypothesis.

[0021]

Examples of the acidic group-containing poly(meth)acrylate include hydroxyl group-containing poly(meth)acrylate and carboxyl group-containing poly(meth)acrylate.

[0022]

(Hydroxy group-containing poly(meth)acrylate)

Hydroxyl group-containing poly(meth)acrylates include hydroxyl group-containing (poly)pentaerythritol poly(alkylene oxide modified or epoxy modified) (meth)acrylate, hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified) ) (meth)acrylate, hydroxyl group-containing (poly)glycerol poly(alkylene oxide modified or epoxy modified) (meth)acrylate, etc. are illustrated.

[0023]

Hydroxyl group-containing (poly)pentaerythritol poly(alkylene oxide modified or epoxy modified) (meth)acrylate

(Poly) pentaerythritol Poly (alkylene oxide modified or epoxy modified) (meth)acrylate is a compound represented by a formula (A') etc.

[Formula 1]

[Wherein, n is an integer of 0 to 2, and R ^b1' to R ^b6' are each independently a hydrogen atom,

[Formula 2]

{Wherein, q is each independently an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit.}

is,

R ^b4' and R ^b5' may have different groups for each structural unit,

In formula (A'), at least two of R ^b1' to R ^b6'

[Formula 3]

{Wherein, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit.}

and at least one of R ^b1' to R ^b6' is a hydrogen atom.]

[0024]

In addition, in the present disclosure, when n is 2 in formula (A'), for example, that "groups may be different for each structural unit",

[Formula 4]

It means that R ^b4A and R ^b4B make different contributions and R ^b5A and R ^b5B also make different contributions.

[0025]

In the present disclosure, "hydroxyl group-containing (poly) pentaerythritol poly (alkylene oxide modified or epoxy modified) (meth) acrylate" means "hydroxyl group-containing pentaerythritol poly (meth) acrylate, hydroxyl group-containing pentaerythritol polyalkylene oxide modified ( meth)acrylate hydroxyl group-containing pentaerythritol polyepoxy-modified (meth)acrylate, hydroxyl group-containing polypentaerythritol poly(meth)acrylate, hydroxyl group-containing polypentaerythritol polyalkylene oxide-modified (meth)acrylate and hydroxyl group-containing polypentaerythritol at least one selected from the group consisting of polyepoxy-modified (meth)acrylates.

[0026]

Examples of the hydroxyl group-containing pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate and pentaerythritol tri(meth)acrylate.

[0027]

Hydroxyl group-containing pentaerythritol polyalkylene oxide-modified (meth)acrylates include pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), and pentaerythritol di(propylene oxide). Modified (meth)acrylate), pentaerythritol tri(propylene oxide modified (meth)acrylate), etc. are illustrated.

[0028]

Examples of the hydroxyl group-containing pentaerythritol polyepoxy-modified (meth)acrylate include pentaerythritol diepoxy (meth)acrylate and pentaerythritol triepoxy (meth)acrylate.

[0029]

Hydroxyl group-containing polypentaerythritol poly(meth)acrylates include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth) An acrylate, tripentaerythritol hepta (meth)acrylate, etc. are illustrated.

[0030]

Hydroxyl group-containing polypentaerythritol polyalkylene oxide-modified (meth)acrylate is dipentaerythritol di(ethylene oxide-modified (meth)acrylate), dipentaerythritol tri(ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra (Ethylene oxide modified (meth)acrylate), dipentaerythritol penta (ethylene oxide modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide modified (meth)acrylate), dipentaerythritol di(propylene oxide modified ( meth) acrylate), dipentaerythritol tri (propylene oxide modified (meth) acrylate), dipentaerythritol tetra (propylene oxide modified (meth) acrylate), dipentaerythritol penta (propylene oxide modified (meth) acrylate) , tripentaerythritol di (ethylene oxide modified (meth) acrylate), tripentaerythritol tri (ethylene oxide modified (meth) acrylate), tripentaerythritol tetra (ethylene oxide modified (meth) acrylate), tripentaerythritol penta (Ethylene oxide modified (meth)acrylate), tripentaerythritol hexa (ethylene oxide modified (meth)acrylate), tripentaerythritol hepta (ethylene oxide modified (meth)acrylate), tripentaerythritol octa (ethylene oxide modified ( meth) acrylate), tripentaerythritol di (propylene oxide modified (meth) acrylate), tripentaerythritol tri (propylene oxide modified (meth) acrylate), tripentaerythritol tetra (propylene oxide modified (meth) acrylate) , tripentaerythritol penta (propylene oxide modified (meth) acrylate), tripentaerythritol hexa (propylene oxide modified (meth) acrylate), tripentaerythritol hepta (propylene oxide modified (meth) acrylate), etc. are illustrated.

[0031]

Hydroxyl group-containing polypentaerythritol polyepoxy-modified (meth) acrylates include dipentaerythritol diepoxy (meth) acrylate, dipentaerythritol triepoxy (meth) acrylate, dipentaerythritol tetraepoxy (meth) acrylate, and dipentaerythritol. Erythritol pentaepoxy (meth) acrylate, tripentaerythritol diepoxy (meth) acrylate, tripentaerythritol triepoxy (meth) acrylate, tripentaerythritol tetraepoxy (meth) acrylate, tripentaerythritol pentaepoxy (meth) Acrylate, tripentaerythritol hexaepoxy (meth)acrylate, tripentaerythritol heptaepoxy (meth)acrylate, etc. are illustrated.

[0032]

Hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate

Hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate is a compound represented by a formula (B') or the like.

[Formula 5]

[Wherein, m is an integer of 0 to 2, and R ^b7' to R ^b10' are each independently a hydrogen atom,

[Formula 6]

{Wherein, q is each independently an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit.}

is,

R ^b9' may be a different group for each structural unit,

At least two of R ^b7' to Rb ^10' in formula (B')

[Formula 7]

{Wherein, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit.}

and at least one of R ^b7' to R ^b10' is a hydrogen atom.]

[0033]

In the present disclosure, "hydroxyl group-containing (poly)trimethylolpropane poly(alkylene oxide modified or epoxy-modified) (meth)acrylate" refers to "hydroxyl group-containing trimethylolpropane poly(meth)acrylate, hydroxyl group-containing trimethylolpropane polyalkylene" Oxide modified (meth)acrylate, hydroxyl group-containing trimethylolpropane polyepoxy modified (meth)acrylate, hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate, hydroxyl group-containing polytrimethylolpropane polyalkylene oxide modified (meth)acrylic rate and at least one selected from the group consisting of hydroxyl group-containing polytrimethylolpropane polyepoxy-modified (meth)acrylate.

[0034]

Examples of the hydroxyl group-containing trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate.

[0035]

Examples of the hydroxyl group-containing trimethylolpropane polyalkylene oxide-modified (meth)acrylate include trimethylolpropane di(ethylene oxide-modified (meth)acrylate) and trimethylolpropane di(propylene oxide-modified (meth)acrylate). .

[0036]

Examples of the hydroxyl group-containing trimethylolpropane polyepoxy-modified (meth)acrylate include trimethylolpropane diepoxy (meth)acrylate.

[0037]

Examples of the hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropane di(meth)acrylate and ditrimethylolpropane tri(meth)acrylate.

[0038]

Hydroxyl group-containing polytrimethylolpropane polyalkylene oxide-modified (meth)acrylates include ditrimethylolpropane di(ethylene oxide-modified (meth)acrylate), ditrimethylolpropane tri(ethylene oxide-modified (meth)acrylate), Ditrimethylolpropane di(propylene oxide modified (meth)acrylate), ditrimethylolpropane tri(propylene oxide modified (meth)acrylate), etc. are illustrated.

[0039]

Examples of the hydroxyl group-containing polytrimethylolpropane polyepoxy-modified (meth)acrylate include ditrimethylolpropane diepoxy (meth)acrylate and ditrimethylolpropane triepoxy (meth)acrylate.

[0040]

Hydroxyl group-containing (poly) glycerin poly (alkylene oxide-modified or epoxy-modified) (meth) acrylate

(Poly) Glycerin Poly (alkylene oxide modified or epoxy modified) (meth)acrylate is a compound represented by a formula (C') etc.

[Formula 8]

[Wherein, p is an integer of 0-7, and R ^b11' to R ^b14' are each independently a hydrogen atom,

[Formula 9]

{Wherein, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit.}

is,

R ^b13' may be a different group for each structural unit,

At least two of R ^b11' to R ^b14' in formula (C')

[Formula 10]

{Wherein, q is an integer of 0 to 16, R ^1′ to R ^3′ are each independently a hydrogen atom or an alkyl group, and R ^1′ may have a different group for each unit.}

and at least one of R ^b11' to R ^b14' is a hydrogen atom.]

[0041]

In the present disclosure, "hydroxyl group-containing (poly)glycerin poly(alkylene oxide modified or epoxy-modified) (meth)acrylate" refers to "hydroxyl group-containing glycerin poly(meth)acrylate, hydroxyl group-containing glycerin polyalkylene oxide modified (meth)acrylic" rate, hydroxyl group-containing polyepoxy modified (meth)acrylate, hydroxyl group-containing polyglycerin poly(meth)acrylate, hydroxyl group-containing polyglycerin polyalkylene oxide modified (meth)acrylate, and hydroxyl group-containing polyglycerin polyepoxy modified (meth) at least one selected from the group consisting of acrylates.

[0042]

As hydroxyl-containing glycerol poly(meth)acrylate, glycerol di(meth)acrylate etc. are illustrated.

[0043]

Examples of the hydroxyl group-containing glycerin polyalkylene oxide-modified (meth)acrylate include glycerin di(ethylene oxide-modified (meth)acrylate) and glycerin di(propylene oxide-modified (meth)acrylate).

[0044]

Examples of the hydroxyl group-containing glycerin polyepoxy-modified (meth)acrylate include glycerin diepoxy (meth)acrylate.

[0045]

Hydroxyl group-containing polyglycerol poly(meth)acrylates include diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, and triglycerin. tetra(meth)acrylate etc. are illustrated.

[0046]

Hydroxyl group-containing polyglycerol polyalkylene oxide-modified (meth)acrylates include diglycerin di(ethylene oxide-modified (meth)acrylate), diglycerin tri(ethylene oxide-modified (meth)acrylate), and triglycerin di(ethylene oxide). Modified (meth)acrylate) triglycerin tri(ethylene oxide modified (meth)acrylate), triglycerin tetra(ethylene oxide modified (meth)acrylate), diglycerin di(propylene oxide modified (meth)acrylate), di Glycerin tri (propylene oxide modified (meth) acrylate) triglycerin di (propylene oxide modified (meth) acrylate), triglycerin tri (propylene oxide modified (meth) acrylate), triglycerin tetra (propylene oxide modified (meth) acrylate) acrylate) and the like.

[0047]

Hydroxyl group-containing polyglycerol Polyepoxy-modified (meth)acrylates include diglycerin diepoxy (meth)acrylate, diglycerin triepoxy (meth)acrylate, triglycerin diepoxy (meth)acrylate, and triglycerin triepoxy (meth)acrylate. ) acrylate, triglycerin tetraepoxy (meth)acrylate, and the like are exemplified.

[0048]

(Carboxyl group-containing poly(meth)acrylate)

Examples of the carboxyl group-containing poly(meth)acrylate include a reaction product with hydroxyl group-containing poly(meth)acrylate and carboxylic acid anhydride.

[0049]

Examples of the carboxylic anhydride include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, itaconic anhydride, and succinic anhydride. do.

[0050]

Poly(meth)acrylate products containing carboxyl groups include Aronix M510 (acid value: 80 to 120 mgKOH/g, Toagosei Co., Ltd. product), Aronix M520 (acid value: 20 to 40 mgKOH/g, Toagosei Co., Ltd. product), etc. This is exemplified.

[0051]

In one embodiment, the acidic group-containing poly(meth)acrylate is preferably a carboxyl group-containing poly(meth)acrylate from the viewpoint of good scratch resistance of the cured product, pentaerythritol tri(meth)acrylate or dipentaerythritol penta A reaction product with (meth)acrylate and carboxylic acid anhydride is more preferable, a reaction product with pentaerythritol tri(meth)acrylate and carboxylic acid anhydride is still more preferable, and a reaction product with pentaerythritol tri(meth)acrylate and succinic anhydride The reactants are particularly preferred.

[0052]

The upper and lower limits of the molecular weight of the acidic group-containing poly(meth)acrylate are 50000, 40000, 30000, 20000, 10000, 5000, 4000, 2000, 1000, 900, 800, 700, 600, 500, 450, 400, 300, 250, 100, 50 and the like are exemplified. In one embodiment, the molecular weight is preferably 50-50000.

[0053]

In the present disclosure, when simply described as "molecular weight", it means either food or a number average molecular weight. When the structure of a compound can be uniquely expressed in a specific chemical formula (ie, the molecular weight distribution is 1), the molecular weight means food. On the other hand, when the structure of a compound cannot be uniquely expressed in a specific chemical formula (ie, the molecular weight distribution is greater than 1), the molecular weight means a number average molecular weight.

[0054]

The upper and lower limits of the acid value of the acid group-containing poly(meth)acrylate are 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 mgKOH/g and the like are exemplified. In one embodiment, the acid value is preferably 10-300 mgKOH/g.

[0055]

The upper and lower limits of the hydroxyl value of the acid group-containing poly(meth)acrylate are 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120 , 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 0 mgKOH/g and the like. In one embodiment, the hydroxyl value is preferably 0 to 280 mgKOH/g, more preferably 10 to 280 mgKOH/g.

[0056]

The upper and lower limits of the number of (meth)acryloyl groups of the acidic group-containing poly(meth)acrylate are 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. are exemplified. In one embodiment, the number is preferably about 2 to 30 pieces.

[0057]

10, 9, 8, 7, 6, 5, 4, 3, 2, 1 piece etc. are illustrated as for the upper limit and a minimum of the number of acidic groups of acidic-group containing poly(meth)acrylate. In one embodiment, the number is preferably 1 to 10.

[0058]

The upper limit and the lower limit of the content of the acidic group-containing poly(meth)acrylate in 100% by mass of the solid content of the coating agent are 70, 65, 60, 57, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 35, 30, 25, 20 mass % etc. are illustrated. In one embodiment, the content is preferably 20 to 70 mass%.

[0059]

<Hollow Inorganic Particles>

The hollow inorganic particles may be used alone or in combination of two or more.

[0060]

Hollow particles can be used without particular limitation as long as they are particles having voids inside. The hollow particles may be any of a spherical shape, a rod shape, a plate shape, a fibrous shape, and an irregular shape.

[0061]

Examples of the hollow inorganic particles include hollow silica particles, hollow aluminosilicate particles, hollow alumina particles, hollow mullite particles, hollow titanium oxide particles, hollow magnesium fluoride particles, and fly ash balloons.

[0062]

In one embodiment, the hollow inorganic particles are preferably modified hollow inorganic particles having a modified surface. Examples of the modified hollow inorganic particles include (meth)acrylic-modified hollow inorganic particles and silicone-modified hollow inorganic particles.

[0063]

40, 35, 30, 25, 20, 15, 10, 5, 1, 0.1, 0.01 mass % etc. are illustrated as the upper limit and lower limit of content of the modified part with respect to 100 mass % of modified hollow inorganic particles. In one embodiment, from the viewpoint of improving the dispersibility of the particles and the scratch resistance of the cured product, the content is preferably about 0.01 to 40 mass%, more preferably 0.1 to 30 mass%, and 1 to 20 mass% more preferably.

[0064]

Products of hollow inorganic particles include Sururia 5320, Sururia 4320, Sururia 4110, Sururia 2320, Sururia 1110, JX1008SIV, JX1009SIV (Nikki Shokyu Hwasung Industrial Co., Ltd. products), Si Linax (Nitetsu High School Co., Ltd.) ) products), etc.

[0065]

The upper and lower limits of the particle diameter of the hollow inorganic particles are exemplified by 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40 nm and the like. In one embodiment, the particle diameter is preferably 40 to 100 nm.

[0066]

The particle diameter of the hollow inorganic particles is measured using a scanning electron microscope (eg, JSM-7800F Prime (manufactured by Japan Electron Co., Ltd.)) and a STEM detector (manufactured by DEBEN UK Ltd.). Specifically, it is measured according to the following steps.

First, the particle sample is diluted with 0.2% of the active ingredient in methyl isobutyl ketone and sufficiently stirred. Next, 1 drop of the dispersion was added to a microgrid with a support film for STEM (Hirezo Carbon HRC-C10 STEM Cu100P grid specification (manufactured by Stem Corporation)) and dried, as a measurement sample.

Next, using a scanning electron microscope, images are acquired at a magnification (for example, 300 k times) that can sufficiently lengthen the particles in the field of view under the condition of an acceleration voltage of 30 kV, and the particle diameters of 50 particles are randomly determined. Measure to determine the particle size based on the number. The particle diameter may be measured manually or using a measuring tool.

[0067]

The upper and lower limits of the refractive index of the hollow inorganic particles are exemplified by 1.5, 1.4, 1.3, 1.2, 1.1, and the like. In one embodiment, the refractive index of the hollow inorganic particles is preferably 1.1 to 1.5.

[0068]

The refractive index of the hollow inorganic particles is 1% by mass of the object to be measured in an active energy ray-curable resin (for example, dipentaerythritol polyacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: product name NK Ester A-9550W) in a solid ratio, A composition containing 10% by mass and 20% by mass was formed into a film, and using an Abbe refractometer (product name “NAR-1T SOLID”, manufactured by Atago Co., Ltd.), the refractive index with respect to the wavelength of the D-line of sodium was measured in accordance with JIS K7142:2014. It measures and calculates by extrapolating to 100 mass % of solid ratio.

[0069]

The upper and lower limits of the content of the hollow inorganic particles in the coating agent solid content 100% by mass are 65, 60, 55, 50, 45, 44, 43, 42, 41, 40, 39, 38, 37, 35, 30, 25, 20 mass % and the like are exemplified. In one embodiment, as for the said content, 20-65 mass % is preferable.

[0070]

<Solid Alumina Particles>

Solid alumina particles can be used individually or in 2 or more types.

[0071]

A solid particle is a particle which does not have an empty hole inside.

[0072]

Alumina means aluminum oxide represented by Al2O3, and forms such as α-type, γ-type, σ-type, and mixtures thereof are known.

[0073]

The solid alumina particles may be any of a spherical shape, a rod shape, a plate shape, a fibrous shape, and an irregular shape.

[0074]

In one embodiment, the solid alumina particles are preferably modified solid alumina particles having a modified surface. Examples of the modified solid alumina particles include (meth)acrylic-modified solid alumina particles and silicone-modified solid alumina particles.

[0075]

Products of solid alumina particles are Aluminsol F-3000 (manufactured by Kawaken Fine Chemicals), Viral AL-7 (manufactured by Taki Chemical Co., Ltd.), NANOBYK-3610 (manufactured by BYK Chemie), Optisol LAA530U (RANCO) products), etc. are exemplified.

[0076]

Examples of the upper and lower limits of the primary particle diameter of the solid alumina particles are 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 7, 3 nm, and the like. In one embodiment, the primary particle diameter is preferably 3 to 110 nm.

[0077]

The primary particle diameter of the solid alumina particles can be measured by the same method as the method for measuring the particle diameter of the hollow inorganic particles.

[0078]

As for the upper limit and lower limit of the secondary particle diameter of solid alumina particle, 110, 100, 90, 80, 70, 60, 55, 50, 45, 40, 35, 30, 25 nm etc. are illustrated. In one embodiment, the secondary particle diameter is preferably 25 to 110 nm.

[0079]

The secondary particle diameter of the solid alumina particles was measured by the following procedure.

First, a sample solution is prepared by diluting the particle sample with 1% of the active ingredient in methyl isobutyl ketone. Next, the prepared sample solution is measured using a nanoparticle diameter measuring device by dynamic light scattering method (product name "Nanotrac UPA-EX150 (Microtrac Bell Co., Ltd. product))." The particle diameter obtained by this measuring method is a volume average particle diameter, and let the value of a median diameter be a particle diameter.

[0080]

15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 mass % etc. are illustrated as for the upper limit and lower limit of content of solid alumina particle in 100 mass % of coating agent solid content. In one embodiment, 2-15 mass % is preferable, and, as for the said content, 6-15 mass % is more preferable.

[0081]

<Perfluoropolyether containing (meth)acryloyl group>

In one embodiment, the coating agent may include a (meth)acryloyl group-containing perfluoropolyether. The (meth)acryloyl group containing perfluoropolyether can be used individually or in 2 or more types.

[0082]

In the present disclosure, the (meth)acryloyl group-containing perfluoropolyether refers to a compound in which one or more (meth)acryloyl groups are bonded to the perfluoropolyether. The perfluoropolyether refers to a compound having perfluoroalkylene ether as a repeating unit.

[0083]

Examples of the (meth)acryloyl group-containing perfluoropolyether include perfluoropolyethers containing (meth)acryloyl groups at both terminals and perfluoropolyethers containing (meth)acryloyl groups at one terminal.

[0084]

Examples of the (meth)acryloyl group-containing perfluoropolyether products include KY-1203 and KY-1207 (manufactured by Shin-Etsu Chemical Industries, Ltd.).

[0085]

In one embodiment, a silicon atom and (meth)acryloyl group-containing perfluoropolyether is preferable from the viewpoint of imparting water and oil repellency, slipperiness, and anti-fingerprint properties to the surface of the cured product. KY-1203 etc. are illustrated as a commercial item of the perfluoro polyether containing a silicon atom and a (meth)acryloyl group.

[0086]

The upper and lower limits of the content of the (meth)acryloyl group-containing perfluoropolyether in 100 mass% of the solid content of the coating agent are 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0 mass%, etc. is exemplified In one embodiment, the content is preferably 0 to 10% by mass.

[0087]

<Photoinitiator>

In one embodiment, the coating agent may include a photoinitiator. A photoinitiator can be used individually or in 2 or more types.

[0088]

Examples of the photopolymerization initiator include a radical photopolymerization initiator, a cationic photopolymerization initiator, and an anionic photopolymerization initiator.

[0089]

Examples of the radical type photopolymerization initiator include an alkylphenone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a hydrogen extraction type photopolymerization initiator, and an oxime ester type photopolymerization initiator.

[0090]

Examples of the alkylphenone-type photopolymerization initiator include benzyldimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl α-hydroxyalkylphenones such as -propan-1-one; α-aminoalkylphenone such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; and the like.

[0091]

Examples of the acylphosphine oxide-type photoinitiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0092]

Examples of the hydrogen extraction type photopolymerization initiator include phenylglyoxylic acid methyl ester.

[0093]

As an oxime ester type photoinitiator, 1,2-octanedione 1-[4-(phenyldio)-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like are exemplified.

[0094]

Cationic photopolymerization initiators include iodonium, (4-methylphenyl)]4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-) and a mixture of propylene carbonate, triarylsulfonium hexafluorophosphate, triarylsulfonium arylsulfonium tetrakis-(pentafluorophenyl)borate and the like are exemplified.

[0095]

Examples of the anionic photopolymerization initiator include a cobaltamine-based compound, o-nitrobenzyl alcohol carbamic acid ester, and oxime ester.

[0096]

10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0 mass % etc. are illustrated as for the upper limit and lower limit of content of a photoinitiator in 100 mass % of coating agent solid content. In one embodiment, the content is preferably 0 to 10% by mass.

[0097]

<Organic solvent>

In one embodiment, the coating agent may include an organic solvent. An organic solvent can be used individually or in 2 or more types.

[0098]

Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, and amide solvents.

[0099]

Examples of the ketone solvent include methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0100]

Examples of the aromatic solvent include toluene and xylene.

[0101]

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol and butanol.

[0102]

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like.

[0103]

The glycol ether solvent is ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl Ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl Ether, ethylene glycol mono-t-butyl ether, etc. are illustrated.

[0104]

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0105]

As a petroleum solvent, Sorvesso #100 (made by Exxon), Sorvesso #150 (made by Exxon), etc. are illustrated.

[0106]

Chloroform etc. are illustrated as a haloalkane solvent.

[0107]

As an amide solvent, dimethylformamide etc. are illustrated.

[0108]

The upper and lower limits of the content of the organic solvent in 100% by mass of the coating agent are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0 mass % etc. are illustrated. In one embodiment, as for the said content, 0-99 mass % is preferable.

[0109]

The upper and lower limits of the mass ratio of the acidic group-containing poly(meth)acrylate and the hollow inorganic particles in the coating agent (the mass of the acidic group-containing poly(meth)acrylate/the mass of the hollow inorganic particles) are 3.5, 3.3, 3, 2.7, 2.5, 2.3, 2, 1.7, 1.5, 1.3, 1, 0.7, 0.5, 0.3 and the like are exemplified. In one embodiment, the mass ratio is preferably 0.3 to 3.5.

[0110]

The upper and lower limits of the mass ratio of the acid group-containing poly(meth)acrylate and the solid alumina particles (the mass of the acid group-containing poly(meth)acrylate/the mass of the solid alumina particles) in the coating agent are 11.7 , 11.5 , 11.3 , 11, 10.7, 10.5, 10.3, 10, 9.7, 9.5, 9.3, 9, 8.7, 8.5, 8.3, 8, 7.7, 7.5, 7.3, 7, 6.7, 6.5, 6.3, 6, 5.7, 5.5, 5.3, 5 , 4.7, 4.5, 4, 3.7, 3.5, 3.3, 3, 2.7, 2.5, 2.3, 2, 1.7, 1.5, 1.3 and the like are exemplified. In one embodiment, the weight ratio is preferably 1.3 to 11.7.

[0111]

The upper and lower limits of the mass ratio of the hollow inorganic particles to the solid alumina particles (mass of hollow inorganic particles/mass of solid alumina particles) in the coating agent are 10.8, 10.5, 10.3, 10, 9.7, 9.5, 9.3, 9, 8.7, 8.5, 8.3, 8, 7.7, 7.5, 7.3, 7, 6.7, 6.5, 6.3, 6, 5.7, 5.5, 5.3, 5, 4.7, 4.5, 4, 3.7, 3.5, 3.3, 3, 2.7, 2.5, 2.3, 2, 1.7, 1.5, 1.3 and the like are exemplified. In one embodiment, the weight ratio is preferably 1.3 to 10.8.

[0129]

<Additives>

The coating agent is an acid group-containing poly(meth)acrylate, hollow inorganic particles, solid alumina particles, (meth)acryloyl group-containing perfluoropolyether, photopolymerization initiator, and an organic solvent. may include

[0113]

Examples of additives include binder resins (acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, etc.), anti-slip agents, slip agents, preservatives, rust inhibitors, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, defoamers, Photosensitizers (amines, quinones, etc.) etc. are illustrated.

[0114]

In one embodiment, as for content of an additive, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated with respect to 100 mass parts of coating agents. In addition, less than 1 part by mass, 0.1 with respect to 100 parts by mass of any of acidic group-containing poly(meth)acrylate, hollow inorganic particles, solid alumina particles (meth)acryloyl group-containing perfluoropolyether, photoinitiator, and organic solvent Less than a mass part, less than 0.01 mass part, 0 mass part, etc. are illustrated.

[0115]

The coating agent is an acidic group-containing poly(meth)acrylate, hollow inorganic particles and solid alumina particles, and if necessary, a (meth)acryloyl group-containing perfluoropolyether, a photopolymerization initiator, an organic solvent and additives are various known means. It can be prepared by dispersing and mixing by In addition, the order of addition of each component is not specifically limited. In addition, various well-known devices (emulsion disperser, ultrasonic dispersion device, etc.) can be used as a dispersion/mixing means.

[0116]

[Coating kit]

The present disclosure provides a coating agent kit comprising a low-reflection coating agent containing 2-15 mass % of solid alumina particles in solid content and an anchor agent containing solid alumina particles.

[0117]

Components, amounts, etc. included in the low-reflection coating agent in the coating kit are exemplified above.

[0118]

In addition, it is possible to prepare a laminate using the coating kit within a time enough that stability is not a problem after the coating kit is manufactured. In this case, the desired laminate is obtained even if the coating kit does not contain an acidic group-containing poly(meth)acrylate. In addition, even without using hollow inorganic particles, low reflectivity can be realized by using a fluorine-based resin or the like.

[0119]

<Anchor system>

Examples of the solid alumina particles contained in the anchor agent include those described above. Solid alumina particles can be used individually or in 2 or more types.

[0120]

The upper and lower limits of the content of the solid alumina particles in 100% by mass of the solid content of the anchor agent are 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 mass % and the like are exemplified. In one embodiment, the content is preferably 2 to 18% by mass.

[0121]

ㆍPoly(meth)acrylate

In one embodiment, the anchoring agent may comprise poly(meth)acrylate. Poly(meth)acrylate can be used individually or in 2 or more types.

[0122]

Examples of the poly(meth)acrylate include acidic group-containing poly(meth)acrylate and urethane poly(meth)acrylate.

[0123]

Examples of the acidic group-containing poly(meth)acrylate include those described above.

[0124]

Examples of the urethane poly(meth)acrylate include a reaction product of a group of compounds containing a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate.

[0125]

Examples of the hydroxyl group-containing poly(meth)acrylate used as a raw material of the urethane poly(meth)acrylate include those described above.

[0126]

In the present disclosure, "polyisocyanate" is a compound having two or more isocyanate groups (-N=C=O).

[0127]

Examples of polyisocyanate include linear aliphatic polyisocyanate, branched chain aliphatic polyisocyanate, cycloaliphatic polyisocyanate, aromatic polyisocyanate and their biuret, isocyanurate (nurate) allophanate, and adduct. do.

[0128]

Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, Decamethylene diisocyanate etc. are illustrated.

[0129]

Examples of the branched chain aliphatic polyisocyanate include diethylpentylene isocyanate, trimethylbutyrene diisocyanate, trimethylpentylene isocyanate, and trimethylhexamethylene diisocyanate.

[0130]

Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, crosslinked alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0131]

As monocyclic alicyclic polyisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethyl Cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, etc. are illustrated.

[0132]

Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate.

[0133]

Examples of the condensed ring alicyclic polyisocyanate include bicyclodecylene diisocyanate.

[0134]

Examples of the aromatic group include a monocyclic aromatic group and a condensed ring aromatic group. In the aromatic group, one or more hydrogen atoms may be substituted with a straight-chain or branched alkyl group.

[0135]

Examples of the monocyclic aromatic group include a phenyl group (phenylene group), tolyl group (torylene group), and mesityl group (mesitylene group). Moreover, a naphthyl group (naphthylene group) etc. are illustrated as a condensed ring aromatic group.

[0136]

Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed cyclic aromatic polyisocyanate.

[0137]

Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m -tetramethylxylylene diisocyanate etc. are illustrated.

[0138]

Examples of the condensed cyclic aromatic polyisocyanate include 1,5-naphthylene diisocyanate and the like.

[0139]

The burette body of polyisocyanate is

Structural formula:

[Formula 11]

[During the ceremony,

n ^b is an integer greater than or equal to 1,

R ^bA to R ^bE are each independently an alkylene group or an arylene group,

R ^bα to R ^bβ are each independently an isocyanate group or

[Formula 12]

(n ^b1 is an integer greater than or equal to 0,

R ^b1 to R ^b5 are each independently an alkylene group or an arylene group,

R ^b' to R ^b" are each independently an isocyanate group or a group of R ^bα to R ^bβ itself.

R ^b4 to R ^b5 , R ^b" may have different groups for each structural unit. ).

R ^{bD to R bE , R bβ may have} different groups for each structural unit.]

The compound represented by and the like are exemplified.

[0140]

As a burette of polyisocyanate, Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (above Asahi Kasei Co., Ltd. product), Desmodule N3200A (a burette of hexamethylene diisocyanate) (above Sumikaco Best) Lourethane Co., Ltd. product) etc. are illustrated.

[0141]

The isocyanurate form of polyisocyanate is

Structural formula:

[Formula 13]

[Wherein, n ⁱ is an integer greater than or equal to 0,

R ^iA to R ^iE are each independently an alkylene group or an arylene group,

R ^iα to R ^iβ are each independently an isocyanate group or

[Formula 14]

(n ⁱ¹ is an integer greater than or equal to 0,

R ⁱ¹ to R ⁱ⁵ are each independently an alkylene group or an arylene group,

R ^i' to R ^i" are each independently an isocyanate group or a group of R ^iα to R ^iβ itself.

R ⁱ⁵ , R ^i" may have different groups for each structural unit.)

to be. R ^iD to R ^iE and R ^iβ may have different groups for each structural unit.]

The compound represented by and the like are exemplified.

[0142]

Commercially available isocyanurate form of polyisocyanate is Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (above manufactured by Asahi Kasei Co., Ltd.), Coronate HXR, Coro Nate HX, Coronate HK (isocyanurate form of hexamethylene diisocyanate) Coronate 2037 (above Tosoh Co., Ltd. product), Takenate D-127N (isocyanurate form of hydrogenated xylene diisocyanate), Take Nate D-131N (isocyanurate form of xylene diisocyanate), Takenate D-204EA-1 (isocyanurate form of tolylene diisocyanate) (above Mitsui Chemicals Co., Ltd. product), VESTANAT T1890/ 100 (isocyanurate form of isophorone diisocyanate) (above Evonik Japan Co., Ltd. product) etc. are illustrated.

[0143]

The allophanate form of polyisocyanate is

The following structural formula:

[Formula 15]

[Wherein n is an integer of 0 or more, R ^A is an alkyl group or an aryl group, R ^B to R ^G are each independently an alkylene group or an arylene group, and R ^α to R ^γ are each independently an isocyanate group or

[Formula 16]

(n1 is an integer of 0 or more, R ¹ to R ⁶ are each independently an alkylene group or an arylene group, and R' to R''' are each independently an isocyanate group or R ^α to R ^γ itself. R ¹ -R ⁴ , R'-R' may have different groups for each structural unit.)

to be. R ^B to R ^E and R ^α to R ^β may have different groups for each structural unit.]

The compound represented by and the like are exemplified.

[0144]

Commercially available products of the allophanate form of polyisocyanate include Coronate 2793 (manufactured by Tosoh Corporation), Takenate D-178N (manufactured by Mitsui Chemicals Co., Ltd.) and the like.

[0145]

The adduct body of polyisocyanate is

Structural formula:

[Formula 17]

[Wherein, n ^ad is an integer of 0 or more, R ^adA to R ^adE are each independently an alkylene group or an arylene group, and R ^ad1 to R ^ad2 are each independently

[Formula 18]

(wherein n ^ad' is an integer greater than or equal to 0,

R ^ad' to R ^ad" are each independently an alkylene group or an arylene group,

R ^ad''' is a group of R ^ad1 ~R ^ad2 itself,

R ^ad' to R ^ad''' may have different groups for each structural unit. )

and R ^adD ~R ^adE , R ^ad2 may have different groups for each structural unit.]

The adduct body of trimethylolpropane and polyisocyanate represented by

the following structural formula

[Formula 19]

[Wherein, n ^ad1 is an integer greater than or equal to 0,

R ^ada to R ^adε are each independently an alkylene group or an arylene group,

R ^adA to R ^adB are each independently

[Formula 20]

(wherein n ^ad1' is an integer greater than or equal to 0,

R ^adδ' to R ^adε' are each independently an alkylene group or an arylene group,

R ^adB' is the group of R ^adA ~R ^adB itself,

R ^adδ' to R ^adε' and R ^adB' may have different groups for each structural unit. )to be.

R ^adδ to R ^adε may have different groups for each structural unit.]

Adduct bodies of glycerin and polyisocyanate represented by , etc. are exemplified.

[0146]

Polyisocyanate adducts include Duranate P301-75E (above manufactured by Asahi Kasei Co., Ltd.), Takenate D110N, Takenate D160N (above manufactured by Mitsui Chemicals Co., Ltd.), Coronate L, Coronate HL (above Tosoh) Note) products), etc. are exemplified.

[0147]

As for the upper limit and the lower limit of the NCO content (NCO%) of the polyisocyanate, 30, 25, 20, 15, 10% or the like is exemplified. In one embodiment, the NCO content (NCO%) is preferably 10 to 30%.

[0148]

As for the upper limit and lower limit of the isocyanate group equivalent of polyisocyanate, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 meq/g etc. are illustrated. In one embodiment, the isocyanate group equivalent is preferably 1 to 10 meq/g.

[0149]

In the present disclosure, the isocyanate group equivalent means the amount of material of the isocyanate group present in 1 g of the solid.

[0150]

The group of compounds used as raw materials of urethane poly(meth)acrylate may include alkylene polyols, polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyolefin polyols, and the like.

[0151]

alkylene polyols

Examples of the alkylene polyol include straight-chain alkylene polyol and branched-chain alkylene polyol.

[0152]

Examples of the straight-chain alkylene polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

[0153]

Branched chain alkylene polyols include neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 1-methylethylene glycol, 1-ethylethylene glycol, Trimethylolpropane, pentaerythritol, etc. are illustrated.

[0154]

Examples of the cycloalkylene polyol include a monocyclic cycloalkylene polyol and a crosslinked cycloalkylene polyol.

[0155]

Examples of the monocyclic cycloalkylene polyol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2'-bis(4-hydroxycyclohexyl)propane.

[0156]

Examples of the cross-linked cycloalkylene polyol include tricyclodecane dimethanol.

[0157]

polyether polyol

In the present disclosure, “polyether polyol” refers to a compound having two or more hydroxyl groups and two or more repeating units including ether bonds. A polyether polyol may use 2 or more types together. In one embodiment, the polyether polyol has the structure

HO-(R ^3' -O-) _n H

(wherein R ^3' is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more).

[0158]

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0159]

polyester polyol

In the present disclosure, "polyester polyol" refers to a compound having two or more hydroxyl groups and two or more repeating units including ester bonds in a molecule. A polyester polyol may use 2 or more types together. In one embodiment, the polyester polyol has the structure

HO-{R ^4a' -OC(O)-R ^4b' -C(O)O} _m -R ^4a' -OH

(Wherein, R ^4a' and R ^4b' are each independently an alkylene group or a cycloalkylene group, and m is an integer of 2 or more).

[0160]

In the present disclosure, "polyester polyol" is a reaction product of polycarboxylic acid or an anhydride thereof and a polyol.

[0161]

As for polycarboxylic acid, dicarboxylic acid etc. are illustrated.

[0162]

Dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3- Methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanoic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, tri Dicarboxylic acids, such as mesic acid, cyclohexane, and dicarboxylic acid, etc. are illustrated.

[0163]

Examples of the polycarboxylic anhydride include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like.

[0164]

Examples of the polyol include the alkylene polyol and the cycloalkylene polyol.

[0165]

polycarbonate polyol

In the present disclosure, “polycarbonate polyol” refers to a compound having, for example, two or more hydroxyl groups and two or more repeating units including carbonate bonds. A polycarbonate polyol may be used independently and may use two or more types together.

[0166]

In one embodiment, the polycarbonate polyol has the structure

HO-{R ^aCarbo -OC(=O)O} _p -R ^bCarbo -OH

(Wherein, R ^aCarbo and R ^bCarbo are each independently an alkylene group or a cycloalkylene group, and p is an integer of 2 or more).

[0167]

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene, and a ring-opening polymer of a cyclic carbonate (such as an alkylene carbonate).

[0168]

Examples of the polyol include the above-mentioned alkylene polyol.

[0169]

Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0170]

acrylic polyol

The acrylic polyol is a polymer of a group of monomers containing a hydroxyl group-containing monomer. The monomer group may include a hydroxyl group-free monomer.

[0171]

polyolefin polyols

The polyolefin polyol is a polyolefin having two or more hydroxyl groups. Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and chlorinated compounds thereof.

[0172]

The upper and lower limits of the number of (meth)acryloyl groups of the poly(meth)acrylate contained in the anchoring agent are 15, 14, 12, 13, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. are exemplified. In one embodiment, 2-15 are preferable and, as for the said number, 3-15 are more preferable.

[0173]

The upper limit and the lower limit of the content of the poly(meth)acrylate in 100% by mass of the anchor agent solid content are 94, 90, 88, 85, 80, 75, 70, 66, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0 mass % etc. are illustrated. In one embodiment, the content is preferably 0 to 94% by mass.

[0174]

· Photoinitiator

In one embodiment, the anchoring agent may include a photoinitiator. A photoinitiator can be used individually or in 2 or more types.

[0175]

Examples of the photopolymerization initiator include those described above.

[0176]

10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0 mass % etc. are illustrated as for the upper limit and lower limit of content of the photoinitiator in 100 mass % of anchor agent solid content. In one embodiment, the content is preferably 0 to 10% by mass.

[0177]

The upper and lower limits of the mass ratio of the poly(meth)acrylate of the anchor agent and the solid alumina particles (mass of poly(meth)acrylate/mass of solid alumina particles) are 47, 45, 43, 41, 40, 39, 37, 35, 33, 31, 30, 29, 27, 25, 23, 21, 20, 19, 17, 15, 13, 11, 10, 9, 8, 7, 5, 4, 3, 2, 1, 0.5, 0.2, 0.1, 0 and the like are exemplified. In one embodiment, the mass ratio is preferably 0 to 47.

[0178]

The upper and lower limits of the mass ratio (mass of photoinitiator/mass of solid alumina particles) of photoinitiator and solid alumina particles in the anchor agent are 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.7 , 0.5, 0.4, 0.3, 0.2, 0.1, 0, and the like are exemplified. In one embodiment, the mass ratio is preferably 0-5.

[0179]

organic solvent

In one embodiment, the anchoring agent may comprise an organic solvent. An organic solvent can be used individually or in 2 or more types.

[0180]

Examples of the organic solvent include those described above.

[0181]

The upper and lower limits of the content of the organic solvent in 100% by mass of the anchor agent solid content are 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0 mass %, etc. are illustrated. In one embodiment, the content is preferably 0 to 80% by mass.

[0182]

Additives for Anchor Agents

The anchor agent may include a solid alumina particle, poly (meth) acrylate, a photoinitiator, and a formulation that does not correspond to any of the organic solvent as an additive for the anchor agent.

[0183]

Examples of the anchor agent additives include those described above.

[0184]

In one embodiment, as for content of the additive of an anchor agent, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated with respect to 100 mass parts of anchor agents. In addition, the content of the anchoring agent additive is less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass with respect to 100 parts by mass of any 100 of solid alumina particles, poly(meth)acrylate, photoinitiator, and organic solvent in the anchoring agent. , 0 parts by mass and the like are exemplified.

[0185]

The anchor agent may be prepared by dispersing and mixing solid alumina particles and, if necessary, poly(meth)acrylate, a photopolymerization initiator, an organic solvent, and an anchor additive additive by various known means. In addition, addition of each component The order is not particularly limited. In addition, various well-known devices (emulsion disperser, ultrasonic dispersion device, etc.) can be used as a dispersion/mixing means.

[0186]

[Cured material]

The present disclosure provides a cured product of the low-reflection coating agent and/or the coating agent kit.

[0187]

The curing conditions are exemplified by the following.

[0188]

[Laminate]

The present disclosure provides a laminate including the cured product.

[0189]

In one embodiment, a cured product layer made of a cured product of the low-reflection coating agent or the coating agent kit is laminated on at least one surface of a substrate. In one embodiment, an anchor agent cured material layer made of a cured material of the anchor agent is laminated on at least one surface of a substrate, and a low reflection coating material cured material layer made of a cured material of a low reflection coating agent is laminated on the anchor agent cured material layer have.

[0190]

Examples of the upper and lower limits of the thickness of the substrate include 125, 120, 110, 100, 90, 75, 50, 25, 10, 9, 5, 1 μm. In one embodiment, the thickness of the substrate is preferably 1 to 125 μm.

[0191]

The upper and lower limits of the thickness of the low-reflection coating agent cured product layer are exemplified by 200, 175, 150, 125, 100, 90, 75, 60, 55 nm. In one embodiment, the thickness of the layer of the cured low-reflection coating agent is preferably 55-200 nm.

[0192]

6, 5, 4, 3, 2, 1 micrometer, etc. are illustrated as for the upper limit and lower limit of the thickness of the anchor agent hardened|cured material layer. In one embodiment, the thickness of the anchor agent cured product layer is preferably 1 to 6 μm.

[0193]

The laminate is manufactured by various known methods. In one embodiment, the method for manufacturing a laminate comprises a process of coating an anchor agent on at least one side of a substrate (anchor agent coating process), a process of applying a low-reflective coating agent to an anchor coating layer (low reflection coating agent application process), active energy The process (active energy ray hardening process) of forming a hardened|cured material layer by irradiating a line|wire is included.

[0194]

It is also called a coating process by combining the anchor agent coating process and the low-reflection coating agent coating process.

[0195]

(coating process)

The coating method is exemplified by bar coater coating, wire bar coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coat coating, offset printing, flexographic printing, screen printing, and the like.

[0196]

The coating amount is not particularly limited. As for the coating amount, the mass after drying is preferably 0.1-30 g/m2.

[0197]

(Active energy ray curing process)

As an active energy ray used for an active energy ray hardening reaction, an ultraviolet-ray, an electron beam, etc. are illustrated. Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and an ultraviolet irradiation device having a metal halide lamp. In addition, the amount of light, the arrangement of the light source, the conveying speed, etc. can be adjusted as needed. In the case of using a high-pressure mercury lamp, it is preferable to cure it at a conveying speed of 2 to 50 m/min, such as lamp 1 having a light quantity of about 80 to 160 W/cm. On the other hand, in the case of an electron beam, it is preferable to harden it under the conditions of about 5-50 m/min conveyance speed by the electron beam accelerator which has an acceleration voltage of about 10-300 kV.

[Example]

[0198]

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the description in the above-described preferred embodiment and the following examples are provided for the purpose of illustration only and not for the purpose of limiting the present invention. Accordingly, the scope of the present invention is not limited to the embodiments specifically described herein or to the examples, but is limited only by the claims. In addition, in each Example and Comparative Example, unless otherwise indicated, numerical values such as parts and % are based on mass.

[0199]

(Example 1-1: Preparation of low-reflection coating agent)

40 parts by mass of acidic group-containing poly(meth)acrylate and carboxyl group-containing poly(meth)acrylate (product name "Aronix M-510" manufactured by Toagosei Co., Ltd.), hollow silica particles (product name Sururia) as hollow inorganic particles 4320", 20 mass % methyl isobutyl ketone sol, Nikkishoku Bai Kasei Co., Ltd. product) 42 mass parts, solid alumina particles (product name "NANOBYK-3610", 30 mass % methoxypropyl acetate, BYK Chemie Co., Ltd. product) ) of 10 parts by mass, (meth)acryloyl group-containing perfluoropolyether (product name "KY-1203", Shin-Etsu Chemical Co., Ltd. 20% by mass) 4 parts by mass, 2-hydroxy-1 as a photoinitiator -{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (product name "Omnirad 127D", manufactured by IGM Resins) 4 mass At the same time as mixing, it was diluted with methyl isobutyl ketone to prepare a low-reflection coating agent having a solid content of 2% by mass.

[0200]

Unless otherwise specified, Example 1 and Comparative Example 1 other than Example 1-1 were performed in the same manner as in Example 1-1 except for changes as shown in the table below.

[0201]

(Stability test of low-reflection coating agent)

The low-reflection coating agent was placed in a 20 mL screw tube and stored at room temperature of 50 ° C., in a light-shielded environment for 1 month, and then the state of the contents of the screw tube was evaluated. The evaluation criteria are as follows.

○: Everything is liquid, and there is no gel-like part at all.

×: Some or all of it is changed to a gel form

Also, as described above, when the hollow particles and the solid alumina particles are present in one system, stability becomes a problem. This is understood from the fact that the stability of the comparative example in which the hollow particles and the solid alumina particles are not present in one system is not bad.

[0202]

[0203]

<Explanation of abbreviations>

Aronix M-306: pentaerythritol triacrylate, manufactured by Toagosei Co., Ltd.

NK ester A-TMMT: pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

NK ester A-DPH: dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd. product

ELCOM V8802: solid silica particles, 40 mass% methyl isobutyl ketone sol, manufactured by Nikkishoku Bai Kasei Co., Ltd.

[0204]

(Preparation Example 1: Preparation of anchor agent)

66 parts by mass of aliphatic urethane acrylate (product name "Movie Set 577", manufactured by Arakawa Chemical Co., Ltd.) 22 parts by mass of dipentaerythritol polyacrylate (product name "NK Ester A-9550W", Shin-Nakamura Chemical Industry Co., Ltd.) 9 parts by mass of solid alumina particles (product name "NANOBYK-3610", 30 mass % methoxypropyl acetate, manufactured by BYK Chemie), 1-[4-(2-hydroxyethoxy)-phenyl]-2 -Hydroxy-methylpropanone (product name "Omnirad 2959", manufactured by IGM Resins) was mixed with 3 parts by mass and diluted with methyl isobutyl ketone to prepare an anchor agent having a solid content of 40% by mass.

[0205]

Unless otherwise specified, Preparation Examples and Comparative Preparation Examples other than Preparation Example 1 were performed in the same manner as in Preparation Example 1 except for changes as shown in the table below.

[0206]

[0207]

(Example 2-1: Preparation of laminate)

The anchor agent prepared above is applied to a polyester (PET) film (product name "Lumira 50U483", manufactured by Toray Co., Ltd.) using a bar coater so that the film thickness after drying becomes 4 μm, and then dried at 80 ° C. for 1 minute. Then, it was cured using a high-pressure mercury lamp (200mJ/cm2) to obtain an anchor film. Apply the low-reflection coating agent prepared above to the anchor agent-coated surface of this anchor film so that the film thickness after drying becomes 100 nm using a bar coater, and after drying at 80 ° C. for 1 minute, under a nitrogen flow, a high-pressure mercury lamp (600 mJ/ cm2) to obtain a laminate.

[0208]

Unless otherwise noted, Example 2 and Comparative Example 2 other than Example 2-1 were performed in the same manner as in Example 2-1 except for changing the composition of the coating agent kit as shown in the table below.

[0209]

The properties of the obtained laminate were evaluated for the following items. The results are shown in the table below.

[0210]

(Total light transmittance and haze)

Based on the standard of JIS K 7361-1 (1997), the total light transmittance and haze of the laminate were measured using a haze meter (product name "HZ-V3", manufactured by Suga Test Instruments Co., Ltd.).

[0211]

(initial water contact angle)

After fixing to a glass plate so that the low-reflection coating surface of the laminate is facing upwards, and after removing the static electricity, 2 μL of deionized water droplets are gently attached using the Kyowa Kaimen Chemical Co., Ltd. contact angle measuring instrument “DropMaster DM500” to measure the contact angle after 1 second (analysis method: θ/2 method).

[0212]

(Water contact angle after steel wool test)

It was installed in a steel wool tester with the low-reflection coating surface of the laminate facing upward, and a steel wool test was performed by 500 reciprocating rubbing at a sliding distance of 4 cm with a load of 1 kg / 4 cm 2 using a steel wool of # 0000. After the steel wool test, the water contact angle was measured for the test site in the same manner as the initial water contact angle.

[0213]

(Steel Wool Resistance)

Install the steel wool tester with the low-reflection coating surface of the laminate facing upward, and perform the steel wool test by rubbing the following number of reciprocations at a sliding distance of 4 cm with a load of 1 kg/4 cm2 using #0000 steel wool. carried out. After the test, the number of wounds generated on the laminate was visually confirmed and evaluated according to the following criteria.

○: 5 wounds or less after 1000 round trips

×: 6 or more wounds after 1000 round trips

[0214]

Claims (5)

acidic group-containing poly (meth) acrylate;
hollow inorganic particles and
comprising solid alumina particles;
A low-reflection coating agent in which the content of the solid alumina particles is 2 to 15% by mass based on the solid content. The low-reflection coating agent according to claim 1, comprising a (meth)acryloyl group-containing perfluoropolyether. A low-reflection coating agent containing 2 to 15 mass % of solid alumina particles in solid content, and
A coating kit comprising an anchor agent comprising solid alumina particles. A cured product of the low-reflection coating agent according to claim 1 or 2 and/or the coating agent kit according to claim 3 . A laminate comprising the cured product according to claim 4.