TW201623484A - Active energy ray-curable resin composition, method for producing same, coating material, coating film, and laminate film - Google Patents

Abstract

Provided are a method for producing an active energy ray-curable resin composition that can prevent the occurrence of a viscosity increase and gelation and that can stably accomplish pulverization and dispersion of inorganic fine particles with high productivity, and an active energy ray-curable resin composition that simultaneously realizes high transparency and excellent appearance (smoothness) of the resulting coating film, as well as a coating material using the composition, a coating film, and a laminate film obtained by forming the coating film. The active energy ray-curable resin composition is characterized by containing an active energy ray-curable resin (A), an antioxidant (C), and inorganic fine particles (D); the method for producing an active energy ray-curable resin composition is characterized in that inorganic fine particles (D) are dispersed into an active energy ray-curable resin (A) in the presence of an antioxidant (C); the coating material is obtained by using the composition; the coating film is obtained by curing the same; and the laminate film has the coating film.

Description

Active energy ray-curable resin composition, method for producing the same, paint, coating film, and laminated film

The present invention relates to a composition capable of suppressing the generation of a gel in a dispersion step and having excellent storage stability, and further relates to an active energy ray hardening which is excellent in both appearance and transparency of a cured coating film. a resin composition comprising: a coating material comprising the resin composition; a coating film comprising the coating material; and a laminated film having the coating film layer.

The active energy ray-curable resin composition of the inorganic fine particle-dispersed type obtained by dispersing the inorganic fine particles in the resin composition is novel as various properties such as improvement in hardness of the coating film, adjustment of refractive index, and impartivity of conductivity. The material is highly regarded. Although it has such a feature, on the other hand, the coating film containing the resin composition in which the inorganic fine particles are dispersed has a disadvantage that the transparency is not preferable to the coating film containing the organic single resin composition. In order to obtain a resin composition having both hardness and transparency of a coating film, it is necessary to disperse the inorganic fine particles pulverized into a smaller particle diameter more stably in the resin.

In general, a method of stably dispersing a resin by pulverizing inorganic fine particles into a smaller particle diameter is considered to be a dispersion using a wet ball mill. However, in this method due to the slip in the grinder When the movable portion is subjected to high shear and a resin component having a polymerizable group such as an acrylonitrile group is used as a dispersion medium, it is polymerized to cause thickening or gelation.

A method of subsequently adding a cerium oxide sol to an active energy ray-curable monomer and an oligomer is known as a method for producing a resin composition of a conventional inorganic fine particle-dispersion type (for example, see Patent Document 1). . However, in this method, since the resin component and the inorganic fine particles are not easily affinityd, the properties such as the hardness or transparency of the coating film cannot reach the required level, and the coating film is phase-separated and easily whitened, and the storage stability is insufficient in the resin composition. There is a problem of coagulation or the like in the substance. Further, the resin composition of the inorganic fine particle dispersion type obtained by such a method may require a concentration step because the nonvolatile content is low, but the concentration of the dispersion tends to cause aggregation of the inorganic fine particles, so that it is difficult to stably perform the process. The operation is also cumbersome.

Therefore, there has been proposed a method of using a stirring tank having a medium filled therein, a rotating shaft, a rotating shaft coaxial with the rotating shaft, and a stirring which is rotated by the rotation of the rotating shaft. a wet ball mill including a blade, a supply port of the slurry provided in the agitation tank, a discharge port of the slurry provided in the agitation tank, and a shaft sealing device disposed at a portion of the rotary shaft passing through the agitation vessel, that is, the shaft seal The device has two mechanical sealing units, and the sealing portion of the two mechanical sealing units is sealed by an external sealing liquid. The wet ball mill is difficult to use even if a polyfunctional acrylate monomer or oligomer is used as a dispersing medium. The thickening or gelation caused by the polymerization of the acrylonitrile group can achieve the pulverization of the inorganic fine particles and the stable dispersion of the resin, and as a result, the stability with time can be easily and efficiently produced, and the nonvolatile content is high. Further, the cured coating film has both an inorganic fine particle-dispersed resin composition having high hardness and high transparency (for example, see Patent Document 2). However, in this method, in terms of high transparency and coating film appearance, the required performance cannot be satisfied.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-242647

[Patent Document 2] International Publication WO2013/047590

An object of the present invention is to provide a method for producing an active energy ray-curable resin composition which can prevent the occurrence of thickening or gelation and which can stably and efficiently produce pulverization and dispersion of inorganic fine particles; The obtained coating film has both an active energy ray-curable resin composition having high transparency and appearance (smoothness), and a coating film using the composition, a coating film, and a laminated film formed by forming the coating film.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that an antioxidant is blended in addition to a polyfunctional acrylate monomer and oligomer as a dispersion medium, whereby polymerization of propylene sulfhydryl groups does not occur. The thickening or gelation caused by the pulverization of the inorganic fine particles and the stable dispersion of the resin are possible, and as a result, the storage stability over time can be easily and efficiently produced, the non-volatile content is high, and the hard coating is applied. A film with inorganic particles dispersed with high transparency and smoothness The lipid composition is completed to the present invention.

That is, the present invention provides an active energy ray-curable resin composition characterized by containing an active energy ray-curable resin (A), an antioxidant (C), and inorganic fine particles (D), and a method for producing the same.

The present invention further provides a coating material comprising the above composition, a coating film obtained by curing the coating material, and a laminated film containing a layer containing the coating film.

According to the present invention, it is possible to provide a method for producing an active energy ray-curable resin composition which can suppress the generation of thickening or gelation and which can stably and efficiently produce pulverization and dispersion of inorganic fine particles; The cured coating film has a composition having high transparency and smoothness, and a coating film using the composition, a coating film, and a laminated film formed by forming the coating film.

P1‧‧‧ stirring tank

Q1‧‧‧ axis

R1‧‧‧ stirring blade

S1‧‧‧ supply port of slurry

T1‧‧‧ slurry discharge

U1‧‧‧ shaft sealing device

1‧‧‧ Shell of shaft seal

2‧‧‧ Screen type separator

3‧‧‧Rotating ring

4‧‧‧Fixed ring

5‧‧‧External sealing fluid supply port

6‧‧‧External sealing fluid drain

7‧‧‧Stirring tank external sealing tank

8‧‧‧ pump

9‧‧‧ formed in the gap between the rotating ring 3 and the fixing ring 4

10‧‧‧ Spring

11‧‧‧Liquid seal space

Y‧‧‧ Wet ball mill

12‧‧‧ Storage tank

13‧‧‧ pump

14‧‧‧Motor

15‧‧‧ product slot

16‧‧‧ valve

17‧‧‧ valve

18‧‧‧ Valves as inlets for compressed air or nitrogen

19‧‧‧Valve

P2‧‧‧ stirring tank

Q2‧‧‧ axis

R2‧‧‧ stirring blade

S2‧‧・Slurry supply port

T2‧‧‧ slurry discharge

U2‧‧‧ shaft sealing device

20‧‧‧ Impeller type separator

21‧‧‧ Shell of shaft seal

22‧‧‧Rotating ring

23‧‧‧Fixed ring

24‧‧‧Liquid seal space

25‧‧‧External sealing fluid supply port

26‧‧‧External sealing fluid drain

27‧‧‧External sealing fluid bath

28‧‧‧ pump

29‧‧‧ A gap formed between the rotating ring 22 and the retaining ring 23

30‧‧‧ Spring

31‧‧‧storage tank

32‧‧‧ pump

33‧‧‧Motor

34‧‧‧Product slot

35‧‧‧ valve

36‧‧‧Valves

37‧‧‧Valve as inlet for compressed air or nitrogen

38‧‧‧Valves

Fig. 1 is a longitudinal sectional view showing a wet ball mill Y used in a method for producing an active energy ray-curable resin composition of the present invention.

Fig. 2 is a longitudinal sectional view showing a shaft sealing device for a wet ball mill Y used in the method for producing an active energy ray-curable resin composition of the present invention.

Fig. 3 is a schematic view showing a circulating dispersion cycle of a raw material slurry of the wet ball mill Y used in the method for producing an active energy ray-curable resin composition of the present invention.

Figure 4 is a composition of an active energy ray-curable resin of the present invention. A longitudinal sectional view of the wet ball mill Z used in the production method.

Fig. 5 is a longitudinal sectional view showing a shaft sealing device of a wet ball mill Z used in the method for producing an active energy ray-curable resin composition of the present invention.

Fig. 6 is a schematic view showing a circulating dispersion cycle of a raw material slurry of the wet ball mill Z used in the method for producing an active energy ray-curable resin composition of the present invention.

[Formation of the Invention]

The dispersion medium of the active energy ray-curable resin (A)-based inorganic fine particles (D) used in the present invention is preferably a coating film which can reduce the curl of the obtained coating film to obtain a coating film having high hardness and excellent curl resistance. The molecular weight is higher and polyfunctional.

Therefore, the active energy ray-curable resin (A) preferably has a weight average molecular weight (Mw) of from 3,000 to 100,000. When the weight average molecular weight (Mw) is 3,000 or more, the curing shrinkage of the obtained coating film is reduced, and the curl resistance is improved. Further, when the weight average molecular weight (Mw) is 100,000 or less, the viscosity is suitable, and the composition can be easily produced. Among them, from the viewpoint of less hardening shrinkage of the coating film and excellent leveling property, it is more preferably in the range of 5,000 to 80,000, and most preferably in the range of 6,000 to 50,000.

Further, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) refer to values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by TOSOH Co., Ltd.

Column; protection of TOSOH Co., Ltd .; column H _XL -H + TOSOH Co. Ltd. TSKgel G5000H _XL + TOSOH Co. Ltd. TSKgel G4000H _XL + TOSOH Co. Ltd. TSKgel G3000H _XL + TOSOH TSKgel G2000H Co., Ltd. _XL

Detector; RI (differential refractometer)

Data Processing: SC-8010 manufactured by TOSOH Co., Ltd.

Standard; polystyrene

Sample; tetrahydrofuran solution converted to 0.4% by mass of resin solid content by microfilter (100 μl)

The active energy ray-curable resin (A) preferably has a (meth) acrylonitrile group in a molecular structure and a (meth) acrylonitrile group equivalent of from 100 g/eq to 600 g/eq. Here, the (meth) acrylonitrile group means an acryl fluorenyl group or a methacryl fluorenyl group, and the (meth) acryl fluorenyl equivalent means the solid of the aforementioned resin (A) per mole of (meth) acrylonitrile group. Component weight (g/eq). When the (meth)acrylonitrile group equivalent of the resin (A) is 100 g/eq or more, the crosslinking density of the obtained coating film is appropriate, and the curl of the coating film by hardening shrinkage can be suppressed. Further, when the (meth)acrylonitrile group equivalent of the resin (A) is 600 g/eq or less, the hardness of the obtained coating film is easily increased. Among the above-mentioned resins (A), the balance of the curl resistance and the hardness of the coating film is preferably from the range of from 150 g/eq to 500 g/eq, and particularly preferably from 170 g/eq. Range of eq~450g/eq.

The active energy ray-curable resin (A) may, for example, be a poly(meth)acrylate (E) having a urethane structure, a poly(meth)acrylate (F) of an acrylic polymer, or an epoxy. Poly(meth)acrylate (G) or the like of the compound.

The poly(meth) acrylate (E) having a urethane structure as described above may, for example, be a polyhydric alcohol compound (e1) and a polyisocyanate compound (e2), and an isocyanate group of polyisocyanate (e2) may be plural. The hydroxy group structure of the alcohol compound (e1) is reacted in an excess amount, and the obtained reaction product is reacted with a hydroxyl group-containing (meth) acrylate compound (e3) to obtain a urethane structure. Acrylate (E1) or poly(meth)acrylate having a urethane structure obtained by reacting a polyisocyanate compound (e2) with a hydroxyl group-containing (meth) acrylate (e3) (E2) ).

The polyol compound (e1) which is a raw material of the poly(meth)acrylate (E1) having a urethane structure may, for example, be ethylene glycol, diethylene glycol, propylene glycol or 1,3-propanediol. 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butyl Glycol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2 An aliphatic diol such as 2,4-trimethyl-1,3-pentanediol; an aliphatic group such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol or pentaerythritol; a polyhydric alcohol; an ether diol such as polyoxyethylene glycol or polyoxypropylene glycol; an alicyclic diol such as 1,4-cyclohexanedimethanol or hydrogenated bisphenol A; By the aforementioned aliphatic diol or aliphatic polyol, with ethylene oxide, propylene oxide, tetrahydrofuran, ethyl epoxypropyl ether, propyl epoxypropyl ether, butyl epoxypropyl ether, benzene Modified polyether diol or polyol obtained by ring-opening polymerization of various cyclic ether bond-containing compounds such as epoxidized propyl ether and allyl epoxypropyl ether; by the aforementioned aliphatic diol or plural a lactone-based polyester diol or a polyhydric alcohol obtained by a condensation reaction of an alcohol with various lactones such as ε-caprolactone; by the aforementioned aliphatic diol or polyol, with malonic acid, succinic acid, and pentane An aliphatic dicarboxylic acid such as an acid, adipic acid, sebacic acid or sebacic acid; an aromatic dicarboxylic acid such as phthalic acid (anhydride), terephthalic acid, isophthalic acid or phthalic acid ; an alicyclic dicarboxylic acid such as hexahydrophthalic acid or 1,4-cyclohexanedicarboxylic acid; tetrahydrophthalic acid, maleic acid (anhydride), fumaric acid, citraconic acid, and y An aliphatic unsaturated dicarboxylic acid such as a benic acid or a glutaconic acid; 1,2,5-hexanetricarboxylic acid, trimellitic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4 -cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylate Tricarboxylic acids and other polycarboxylic acids such as various kinds of obtained polyester diol or polyol co-condensation. These may be used alone or in combination of two or more.

Examples of the polyisocyanate compound (e2) which is a raw material of the poly(meth)acrylate (E1) and (E2) having a urethane structure include various diisocyanate monomers and an amine group in the molecule. An adduct-type polyisocyanate compound at an acid ester-bonded site, a nurate polyisocyanate compound having an isomeric cyanate ring structure in the molecule, and the like.

The diisocyanate monomer may, for example, be butane-1,4-diisocyanate, hexamethylene diisocyanate or 2,2,4-trimethylhexamethylene. Aliphatic diisocyanate such as isocyanate, 2,4,4-trimethylhexamethylene diisocyanate, benzodimethyl diisocyanate or m-tetramethylbenzene diisocyanate; cyclohexane-1,4-di Isocyanate, isophorone diisocyanate, quaternary acid diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, etc. Alicyclic diisocyanate; 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-diphenyl An aromatic diisocyanate such as a diisocyanate, a dialkyldiphenylmethane diisocyanate, a tetraalkyldiphenylmethane diisocyanate, a meta-phenylene diisocyanate, a p-phenylene diisocyanate or a benzylidene diisocyanate.

The adduct-type polyisocyanate compound having a urethane-bonding site in the molecule can be obtained, for example, by reacting a diisocyanate monomer with a polyol compound. The diisocyanate monomer to be used in the reaction may be any of the above various diisocyanate monomers, and these may be used alone or in combination of two or more. In addition, the polyol compound to be used for the reaction is exemplified by various polyol compounds which are exemplified as the polyol compound (e1).

The urethane-type polyisocyanate compound having an isomeric cyanate ring structure in the above molecule can be obtained, for example, by reacting a diisocyanate monomer with a monool and/or a diol. The diisocyanate monomer to be used in the reaction may be any of the above various diisocyanate monomers, and these may be used alone or in combination of two or more. Further, examples of the monool used in the reaction include hexanol, 2-ethylhexanol, octanol, and anthracene. Alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecanol, n-hexadecanol, n-octadecyl alcohol, n-nonadecanol, eicosyl alcohol, 5-ethyl 2-nonanol, trimethylnonanol, 2-hexyldecyl alcohol, 3,9-diethyl-6-tridecyl alcohol, 2-isoheptylisoundecyl alcohol, 2-octyldodecanol, Examples of the diol include 2-mercaptotetradecyl alcohol and the like, and various diols as the polyol compound (e1) are exemplified. These monools or diols may be used alone or in combination of two or more.

The hydroxyl group-containing (meth) acrylate compound (e3) which is a raw material of the poly(meth) acrylate (E1) and (E2) having a urethane structure, for example, (meth)acrylic acid Hydroxy mono (methyl) such as 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Acrylate; hydroxydi(meth)acrylate such as glycerol di(meth)acrylate or trimethylolpropane di(meth)acrylate; hydroxyl group such as pentaerythritol tri(meth)acrylate Tris(meth)acrylate; hydroxypenta(meth)acrylate such as dipentaerythritol penta (meth) acrylate or sorbitol penta (meth) acrylate. These may be used alone or in combination of two or more.

The poly(meth)acrylates (E1) and (E2) having a urethane structure may be used alone or in combination of two or more.

For the production of the above poly(meth)acrylates (E1) and (E2) having a urethane structure, for example, tin (II) octoate or zinc octoate (II) may be suitably used in a temperature range of 20 to 120 ° C. The urethane-catalyzed catalyst is used. The reaction may be carried out under solvent-free conditions, or a solvent which is inert to a hydroxyl group or an isocyanate group such as p-toluene or xylene, methyl ethyl ketone or methyl isobutyl ketone.

The poly(meth)acrylate (F) of the acrylic polymer may, for example, be a (meth)acrylic polymer having a (meth)acrylonyl group and a carboxyl group (f2) and having an epoxy group. The poly(meth)acrylate (f1) of the acrylic polymer obtained by the addition reaction of the material (f1), and the monomer (f4) having a (meth)acryloyl group and an epoxy group have a carboxyl group ( a poly(meth)acrylate (f2) of an acrylic polymer obtained by an addition reaction of a methyl)acrylic polymer (f3), and a monomer having a (meth)acrylonium group and an isocyanate group ( F6) A poly(meth)acrylate (F3) of an acrylic polymer obtained by subjecting a (meth)acrylic polymer (f5) having a hydroxyl group to an addition reaction.

First, the poly(meth)acrylate (F1) of the above acrylic polymer will be described.

The (meth)acrylic polymer (f1) having an epoxy group used as a raw material of the poly(meth)acrylate (F1) of the acrylic polymer, for example, may have a (meth) acrylonitrile group and The homopolymerization reaction of the epoxy group-polymerizable monomer (H) or the copolymerization reaction with another polymerizable monomer (I).

The polymerizable monomer (H) having a (meth)acryl fluorenyl group and an epoxy group, which is used as a raw material of the (meth)acrylic polymer (f1) having an epoxy group, may, for example, be a methyl group. ) Glycidyl acrylate, g-propyl α-ethyl (meth) acrylate, g-propyl α-n-propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate , (meth)acrylic acid-3,4-epoxybutyl ester, (meth)acrylic acid-4,5-epoxypentyl ester, (meth)acrylic acid-6,7-epoxypentyl ester, α-ethyl (meth)acrylic acid-6,7-epoxypentyl ester, β-methylepoxypropyl (meth) acrylate, (meth)acrylic acid-3,4-epoxy ring The hexyl ester and the lactone are modified with (meth)acrylic acid-3,4-epoxycyclohexyl ester, vinylcyclohexene oxide and the like. These may be used alone or in combination of two or more. Among these, the (meth)acrylic acid ring is particularly preferred from the viewpoint of easily adjusting the (meth)acryl oxime equivalent of the poly(meth)acrylate (F1) of the acrylic polymer to the above preferred range. Oxypropyl propyl ester, α-ethyl (meth) acrylate propyl acrylate, and α-n-propyl (meth) acrylate propyl acrylate.

The other polymerizable monomer (I) used as a raw material of the (meth)acrylic polymer (f1) having an epoxy group may, for example, be methyl (meth)acrylate or (meth)acrylic acid Ester, propyl (meth) acrylate, n-butyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) acrylate Octyl ester, decyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (methyl) (meth) acrylate having a carbon number of 1 to 22, such as stearyl acrylate, octadecyl (meth) acrylate, or behenyl (meth) acrylate; (meth) acrylate ring a (meth) acrylate having an alicyclic alkyl group such as an ester, isodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate or dicyclopentenyloxyethyl (meth) acrylate; Benzomethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy (meth)acrylate Diethylene glycol, (methyl) Acid 2-hydroxy-3-phenoxypropyl acrylate, etc. having an aromatic ring-containing (meth) acrylate; (meth) acrylate, hydroxy ethyl acrylate; (meth) acrylate, hydroxy propyl Ester, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; lactone modified hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. Acrylate having a hydroxyalkyl group having a polyolefin diol group (meth) acrylate or the like; dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate , unsaturated dicarboxylic acid esters such as dibutyl formate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate; styrene, α-methyl styrene, a styrene derivative such as chlorostyrene; a diene compound such as butadiene, isoprene, pentadiene or dimethylbutadiene; a vinyl halide or a vinylidene halide such as vinyl chloride or vinyl bromide; An unsaturated ketone such as methyl vinyl ketone or butyl vinyl ketone; a vinyl ester such as vinyl acetate or vinyl butyrate; a vinyl ether such as methyl vinyl ether or butyl vinyl ether; and propylene; Cyanide such as nitrile, methacrylonitrile or dicyandiethylene; acrylamide or its alkyd substituted decylamine; N-phenylmaleimide, N-cyclohexylmale An N-substituted maleimide such as fluorene, such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropene or hexafluoropropylene. Olefins; such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluoroethyl a (per)fluoroalkyl group having a carbon number of from 1 to 18, the alkenyl ether or the (per)fluoroalkyl group of pentafluoropropyl trifluorovinyl ether. Perfluorovinyl ether; such as 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-eight Fluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate or perfluoroethyl oxyethyl (meth) acrylate (per) fluoroalkane a (per)fluoroalkyl (meth) acrylate having a carbon number of from 1 to 18; a decyl-containing (meth) acrylate such as γ-methacryloxypropyltrimethoxydecane; N,N-Dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate or N,N-diethylaminopropyl (methyl) An N,N-dialkylaminoalkyl (meth) acrylate such as an acrylate. These may be used alone or in combination of two or more. Among these, based on the ease of adjusting the (meth) acryl of the poly(meth) acrylate (G1) of the above acrylic polymer to the above preferred range, the resulting coating film does not become too hard and brittle. The viewpoint is preferably a (meth) acrylate having an alkyl group having 1 to 22 carbon atoms, and a (meth) acrylate having an alkyl group having an alicyclic group, more preferably an alkyl group having 1 to 22 carbon atoms. Base (meth) acrylate. Particularly preferred are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and tertiary butyl (meth)acrylate.

The (meth)acrylic polymer (f1) having an epoxy group may be a homopolymer of a polymerizable monomer (H) having a (meth)acryl fluorenyl group and an epoxy group, as described above. It is a copolymer with other polymerizable monomer (I). Among these, in order to use the epoxy of the obtained acrylic polymer (f1) The amount is adjusted to a preferred range, and is preferably a mass ratio of the two when copolymerizing [polymerizable monomer (H) having (meth)acrylonyl group and epoxy group]: [other polymerization sheets The body (I)] is a polymer obtained by copolymerizing a ratio of 25 to 100 parts by mass: 75 to 0 parts by mass, more preferably 40 to 100 parts by mass: 60 to 0 parts by mass.

The epoxy equivalent of the epoxy group-containing (meth)acrylic polymer (f1) is adjusted to 100 to 600 g based on the propylene equivalent of the poly(meth)acrylate (F1) of the obtained acrylic polymer. The range of the range of /eq is in the range of 80 to 500 g/eq, preferably in the range of 120 to 470 g/eq, and particularly preferably in the range of 150 to 400 g/eq.

The (meth)acrylic polymer (f1) having an epoxy group can be produced by, for example, addition polymerization in the presence of a polymerization initiator in a temperature range of from 80 ° C to 150 ° C. A random copolymer, a block copolymer, a graft copolymer and the like are mentioned. The copolymerization method may be a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like. Among these, based on the viewpoint that the reaction can be continuously carried out, and the reaction between the (meth)acrylic polymer (f1) and the polymerizable monomer (f2) having a (meth)acrylonyl group and a carboxyl group is continued. Preferably, it is a solution polymerization method.

When the solvent used for the production of the epoxy group-containing (meth)acrylic polymer (f1) is subjected to a solution polymerization method, when the reaction temperature is measured, the boiling point is 80 ° C or higher, and for example, a methyl group is mentioned. Ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, a ketone solvent such as ethyl n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone or isophorone; n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether , ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, two An ether solvent such as an alkane; n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ester-based solvent such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxy propionate; Propanol, n-butanol, isobutanol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methyl-3-methoxybutanol, etc. Alcohol-based solvent; hydrocarbon-based solvent such as toluene, xylene, Solvesso 100, Solvesso 150, Swasol 1800, Swasol 310, Isopar E, Isopar G, Exxon Naphtha 5, Exxon Naphtha 6. These may be used alone or in combination of two or more.

Among the above-mentioned solvents, a ketone system such as methyl ethyl ketone or methyl isobutyl ketone is preferred from the viewpoint that the solubility of the (meth)acrylic polymer (f1) having the epoxy group obtained is excellent. Solvent.

The catalyst used for the production of the epoxy group-containing (meth)acrylic polymer (f1) may, for example, be 2,2'-azobisisobutyronitrile or 2,2'-azobis- An azo compound such as (2,4-dimethylvaleronitrile) or 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, Lauryl peroxide, peroxyisobutyrate, tertiary butyl ester, peroxyethylhexanoate, tertiary butyl ester, 1,1'-bis-(tri-butylperoxy)cyclohexane, tertiary pentyl Organic peroxygen such as oxy-2-ethylhexanoate or tertiary hexylperoxy-2-ethylhexanoate Compounds and hydrogen peroxide.

When a peroxide is used as a catalyst, a peroxide may be used together with a reducing agent to form a redox type initiator.

The monomer (f2) having a (meth) acrylonitrile group and a carboxyl group used as a raw material of the poly(meth)acrylate (F1) of the acrylic polymer may, for example, be (meth)acrylic acid; β-carboxylate Ethyl (meth) acrylate, 2-propenyl methoxyethyl succinic acid, 2-propenyl methoxyethyl phthalic acid, 2-propenyl methoxyethyl hexahydrophthalic acid, and the like An unsaturated monocarboxylic acid having an ester bond such as a lactone modified product; maleic acid; a polyfunctional (meth)acrylic acid having a hydroxyl group such as an acid anhydride such as succinic anhydride or maleic anhydride and neopentyl alcohol triacrylate A polyfunctional (meth) acrylate containing a carboxyl group obtained by reacting an ester monomer. These may be used alone or in combination of two or more. Among these, (meth)acrylic acid is preferred from the viewpoint of easily adjusting the (meth)acrylonitrile group equivalent of the poly(meth)acrylate (F1) of the acrylic polymer to the above preferred range. Β-carboxyethyl (meth) acrylate, and 2-propenyl methoxyethyl succinic acid, particularly preferably (meth)acrylic acid.

The poly(meth) acrylate (E1) of the acrylic polymer is a monomer (f1) having an epoxy group and a monomer having a (meth) acrylonitrile group and a carboxyl group (f2) ) The reaction comes. This reaction can be carried out by, for example, polymerizing a (meth)acrylic polymer (f1) having an epoxy group by a solution polymerization method, and adding a monomer (f2) having a (meth)acrylonyl group and a carboxyl group to the reaction system. Further, it is carried out by a method such as a catalyst such as triphenylphosphine in a temperature range of 80 to 150 °C. The poly(meth)acrylate (F1) of the acrylic polymer preferably has an acrylonitrile equivalent of 100~. In the range of 600 g/eq, this can be adjusted depending on the reaction ratio of the (meth)acrylic polymer (f1) having an epoxy group to the monomer (f2) having a (meth)acrylinyl group and a carboxyl group. Usually, the carboxyl group in the monomer (f2) having a (meth)acryloyl group and a carboxyl group is 1 mol with respect to the epoxy group in the (meth)acrylic polymer (f1) having an epoxy group. The reaction of the range of 0.4 to 1.1 moles is carried out, whereby the (meth)acryl oxime equivalent of the poly(meth)acrylate (F1) of the obtained acrylic polymer can be adjusted to the above preferred range.

The poly(meth)acrylate (F1) of the acrylic polymer thus obtained has a hydroxyl group formed by a reaction of a carboxyl group and an epoxy group in a molecule. For the purpose of adjusting the propylene oxime equivalent of the poly(meth) acrylate (F1) of the acrylic polymer to a preferred range, a monomer having one isocyanate group and (meth) acryl oxime group is required as needed (J The poly(meth)acrylate (F1') of the acrylic polymer obtained by the addition reaction of the hydroxyl group can also be used as the compound (A) of the present invention.

The monomer (J) having one isocyanate group and (meth) acrylonitrile group may, for example, be a compound represented by the following formula 1, and may have one isocyanate group and one (meth) acrylonitrile group. Monomer, monomer having one isocyanate group and two (meth)acryl fluorenyl groups, monomer having one isocyanate group and three (meth) acrylonitrile groups, having one isocyanate group and four (methyl group) a monomer of an acrylonitrile group, a monomer having one isocyanate group and five (meth) acrylonitrile groups, and the like.

In the formula (1), R ₁ is a hydrogen atom or a methyl group. R ₂ is an alkylene group having 2 to 4 carbon atoms. n represents an integer from 1 to 5.

As an example of a specific product of the monomer (J) having a (meth) acrylonitrile group and an isocyanate group, 2-propenyloxyethyl isocyanate (trade name: Showa Denko Co., Ltd.) Karenz AOI", etc.), 2-methylpropenyloxyethyl isocyanate (trade name: "Karenz MOI" manufactured by Showa Denko Co., Ltd.), 1,1-bis(acryloxymethyl)ethyl isocyanate (trade name: "Karenz BEI" manufactured by Showa Denko Co., Ltd.). As another example, a compound obtained by adding a hydroxyl group-containing (meth) acrylate compound to one isocyanate group of a diisocyanate compound can be mentioned. The diisocyanate compound to be used in the reaction is exemplified by various diisocyanate monomers which are exemplified as the polyisocyanate compound (e1). In addition, the hydroxyl group-containing (meth) acrylate compound used in the reaction is exemplified by various hydroxyl group-containing (meth)acrylic acids which are exemplified as the hydroxyl group-containing (meth) acrylate compound (e3). Ester compound. These may be used alone or in combination of two or more. Among these, from the viewpoint of easily adjusting the (meth)acryl oxime equivalent of the poly(meth) acrylate (F1') of the obtained acrylic polymer to the above preferred range, it is preferably (methyl). 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate A hydroxy mono(meth)acrylate such as 2-hydroxy-3-phenoxypropyl ester is particularly preferably 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

The reaction of the poly(meth)acrylate (F1) of the aforementioned acrylic polymer with the monomer (J) having one isocyanate group and (meth)acryloyl group can be carried out, for example, by poly(methyl) in an acrylic polymer. In the acrylate (F1), a monomer (I) having a (meth) acrylonitrile group and an isocyanate group is added dropwise, and the mixture is heated to 50 to 120 ° C or the like.

In the poly(meth)acrylates (F1) and (F1') of the aforementioned acrylic polymer, more hydroxyl groups are contained in the molecule, and the interaction with the inorganic particles (D) can increase the inorganic particles. The dispersibility of (D) is preferably a poly(meth)acrylate (F1) of the above acrylic polymer.

Next, the poly(meth)acrylate (F2) of the above acrylic polymer will be described.

The (meth)acrylic polymer (f3) having a carboxyl group used as a raw material of the poly(meth)acrylate (F2) of the acrylic polymer can be, for example, a (meth)acryloyl group and a carboxyl group. The homopolymerization reaction of the polymerizable monomer (K) or the copolymerization reaction with another polymerizable monomer (L).

The polymerizable monomer (K) having a (meth)acryl fluorenyl group and a carboxyl group, which are used as a raw material of the (meth)acrylic polymer (f3) having a carboxyl group, is exemplified as Each of the monomers of the methyl (meth) fluorenyl group and the carboxyl group (f2) may be used alone or in combination of two or more.

As the aforementioned (meth)acrylic polymer having a carboxyl group The other polymerizable monomer (L) used as the raw material of the material (f3) may, for example, be a monomer which is exemplified as the other polymerizable monomer (I), and these may be used alone or in combination. Use two or more.

The (meth)acrylic polymer (f3) having a carboxyl group may be a homopolymer of a polymerizable monomer (K) having a (meth)acryl fluorenyl group and a carboxyl group, or may be a polymerizable single with another group. a copolymer of the body (L). In the above, when the epoxy equivalent of the obtained acrylic polymer (f3) is adjusted to a preferred range, the mass ratio of both of them in the copolymerization [having polymerizability of (meth)acryloyl group and carboxyl group) Monomer (K)]: [Other polymerizable monomer (L)] is preferably in the range of 25 to 100 parts by mass: 75 to 0 parts by mass, more preferably 40 to 100 parts by mass: 60 to 0% by mass. The scope of the share.

The (meth)acrylic polymer (f3) having a carboxyl group can be produced, for example, under the same conditions as the production of the (meth)acrylic polymer (f1) having the epoxy group.

The monomer (f4) having a (meth) acrylonitrile group and an epoxy group, which is used as a raw material of the poly(meth)acrylate (F2) of the acrylic polymer, is exemplified as the above-mentioned (for example) Each of the various monomers of the polymerizable monomer (G) which is a methyl propylene group and an epoxy group may be used alone or in combination of two or more.

The poly(meth)acrylate (F2) of the acrylic polymer is a monomer having a carboxyl group (f) and a monomer having a (meth)acrylonyl group and an epoxy group (f4) ) The reaction comes. This reaction can be carried out by, for example, polymerizing a (meth)acrylic polymer (f1) having an epoxy group by a solution polymerization method, and adding a monomer (f2) having a (meth)acrylonyl group and a carboxyl group to the reaction system. Under the temperature of 80~150 °C, make appropriate It is carried out by a method such as a catalyst such as triphenylphosphine. The acryl oxime equivalent of the poly(meth) acrylate (F2) of the acrylic polymer is preferably in the range of 100 to 600 g/eq, but it may be based on a (meth)acrylic polymer (f3) having a carboxyl group and having The reaction ratio of the (meth)acryloyl group and the epoxy group monomer (f4) is adjusted. Usually, the epoxy group in the monomer (f4) having a (meth)acryl fluorenyl group and an epoxy group is 1 mol with respect to the carboxyl group in the (meth)acrylic polymer (f3) having a carboxyl group. The reaction is carried out in such a manner as to range from 0.4 to 1.1 mol, whereby the obtained propylene oxime equivalent of (meth) acrylate (F2) can be adjusted to the above preferred range.

The poly(meth)acrylate (F2) of the acrylic polymer thus obtained has a hydroxyl group formed by a reaction of a carboxyl group and an epoxy group in a molecule. For the purpose of adjusting the propylene oxime equivalent of (meth) acrylate (F1) to a preferred range, it is also possible to use the above-mentioned one having an isocyanate group and (meth) propylene. A poly(meth)acrylate (F2') of an acrylic polymer obtained by subjecting a hydroxyl group monomer (J) to an addition reaction of the hydroxyl group. This reaction can be carried out under the same conditions as the reaction of the poly(meth)acrylate (F1) of the above acrylic polymer and the monomer (J) having one isocyanate group and (meth)acryloyl group.

Next, the poly(meth)acrylate (F3) of the above acrylic polymer will be described.

The (meth)acrylic polymer (f5) having a hydroxyl group used as a raw material of the poly(meth)acrylate (F3) of the acrylic polymer can be, for example, a (meth)acryloyl group and a hydroxyl group. a homopolymerization reaction of a polymerizable monomer (M) or a copolymerization reaction with another polymerizable monomer (N) Got it.

The polymerizable monomer (M) having a (meth) acrylonitrile group and a hydroxyl group used as a raw material of the (meth)acrylic polymer (f5) having a hydroxyl group may, for example, be 2-hydroxyethyl acrylate. 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate , 2,3-dihydroxypropyl methacrylate, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the hydroxyl value of the obtained (meth)acryl-based polymer (f5), 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferable. By designing the hydroxyl value of the (meth)acrylic polymer (f5) to be high, and leaving the hydroxyl group in the poly(meth)acrylate (F3) of the finally obtained acrylic polymer, it is possible to The dispersibility of the inorganic fine particles (D) is improved.

The other polymerizable monomer (N) used as a raw material of the (meth)acrylic polymer (f5) having a hydroxyl group is exemplified by various examples of the other polymerizable monomer (I). The monomers may be used singly or in combination of two or more.

The (meth)acrylic polymer (f5) having a hydroxyl group may be a homopolymer of a polymerizable monomer (M) having a (meth)acryl fluorenyl group and a hydroxyl group, or may be a polymerizable single with other monomers. a copolymer of the body (N). In the above, when the epoxy equivalent of the obtained acrylic polymer (f3) is adjusted to a preferred range, the mass ratio of both of them in the copolymerization [having polymerizability of (meth)acrylonyl group and hydroxyl group) Monomer (M)]: [Other polymerizable monomer (N)] is preferably in the range of 25 to 100 parts by mass: 75 to 0 parts by mass, more preferably 30 to 70 parts by mass: 70 to 30 parts by mass The scope of the share.

The (meth)acrylic polymer (f5) having a hydroxyl group can be produced, for example, at the same temperature and catalyst conditions as the production of the (meth)acrylic polymer (f1) having the epoxy group.

The solvent used for the production of the (meth)acrylic polymer (f5) having a hydroxyl group is exemplified by the production of the (meth)acrylic polymer (f1) having the epoxy group. Various solvents for the solvent.

The monomer (f6) having a (meth)acryl fluorenyl group and an isocyanate group, which is used as a raw material of the poly(meth) acrylate (F3) of the acrylic polymer, is exemplified as Various compounds of methyl (meth) fluorenyl group and one isocyanate group monomer (J). These may be used alone or in combination of two or more. Among these, from the viewpoint that a poly(meth)acrylate (F3) of an acrylic polymer is a more functional compound and a coating film of higher hardness can be obtained, it is preferable to have two or more in one molecule (A) The propylene group is, in particular, preferably 1,1-bis(acryloxymethyl)ethyl isocyanate.

The poly(meth)acrylate (F3) of the above acrylic polymer may be a (meth)acrylic polymer (f5) having a hydroxyl group and a monomer having a (meth)acrylonitrile group and an isocyanate group ( F6) obtained by reaction. This reaction can, for example, polymerize a (meth)acrylic polymer (f5) having a hydroxyl group by solution polymerization, and a monomer (f6) having a (meth)acrylonitrile group and an isocyanate group in the reaction system. It is added dropwise, and it is carried out by using a catalyst such as tin(II) octoate as appropriate at a temperature of 50 to 120 °C. The poly(meth)acrylate (F3) of the acrylic polymer preferably has an acrylonitrile equivalent of from 100 to 600 g/eq, but this may be based on The reaction ratio of the hydroxyl group-containing (meth)acrylic polymer (f5) to the monomer (f6) having a (meth)acrylonium group and an isocyanate group is adjusted. Usually, the isocyanate group in the monomer (f6) having a (meth)acryl fluorenyl group and an isocyanate group is 1 mol with respect to the hydroxyl group in the (meth)acrylic polymer (f5) having a hydroxyl group. The acryl oxime equivalent of the poly(meth) acrylate (F3) of the obtained acrylic polymer can be adjusted to the above preferred range by reacting the number of ears in a range of 0.7 to 1.2 mol. Further, the isocyanate group in the monomer (f6) having a (meth)acryl fluorenyl group and an isocyanate group with respect to the hydroxyl group 1 mol in the (meth)acrylic polymer (f5) having a hydroxyl group The ratio of the number of the ears is in the range of 0.7 to 0.9 mol to cause the reaction, whereby the poly(meth)acrylate (F3) of the obtained acrylic polymer can have a hydroxyl group in the molecular structure, and the inorganic fine particles can be improved ( The dispersing ability of D) is therefore preferred.

The poly(meth)acrylates (F1), (F2), and (F3) of the acrylic polymer may be used alone or in combination of two or more. Among these, the poly(meth)acrylates (F1) and (F2) of the acrylic polymer have a higher affinity in the molecule, and therefore the affinity of the inorganic fine particles (D) to the metal oxide surface is better. The viewpoint of excellent storage stability of the dispersion is preferred. Among them, from the viewpoint of simpler synthesis, a poly(meth)acrylate (F1) of an acrylic polymer is preferred, and a (meth)acrylic acid is preferably used for the use of glycidyl (meth)acrylate. A reaction product obtained by subjecting an epoxy group-containing (meth)acrylic polymer (f1) to an addition reaction.

The poly(meth)acrylates (F1) and (F2) of the acrylic polymer preferably have a hydroxyl value of from 90 to 280 g/eq, more preferably from 140 to 280. A range of 270 g/eq.

The poly(meth)acrylate (G) of the epoxy compound may, for example, be a monomer having a (meth)acryl fluorenyl group and a carboxyl group (g2) to the above-mentioned (meth)acrylic polymer having an epoxy group. The compound (g1) having an epoxy group in the molecular structure other than (f1) is obtained by an addition reaction.

The compound (g1) having an epoxy group in the molecular structure may, for example, be propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol or tetra. Various diols such as ethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, neopentyl glycol hydroxypivalate, bisphenol A, bisphenol F, ethoxylated bisphenol A, etc.; a modified diol obtained by modifying a hydroxyl group of various diols with ethylene glycol or propylene glycol; trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, glycerin, etc. a trihydric alcohol; a modified trihydric alcohol obtained by modifying a hydroxyl group of the above various triols with ethylene glycol or propylene glycol; a polyfunctional aromatic polyol such as a phenol novolac or a cresol novolac; a modified polyfunctional aromatic polyol obtained by modifying a hydroxyl group of a polyhydric alcohol with ethylene glycol or propylene glycol; and a hydrogenated type of epichlorohydrin or the like which is a polyfunctional aromatic polyol and a modified polyfunctional polyol. A hydroxyl group such as a polyfunctional alicyclic polyol is added, or a bisphenol A or a bisphenol F is used. Diglycidyl ether of bisphenol A and bisphenol type epoxy resin obtained by the polymerization.

The monomer (g2) having a (meth) acrylonitrile group and a carboxyl group is exemplified by various compounds which are exemplified as the monomer (f2) having a (meth) acrylonitrile group and a carboxyl group.

Poly(meth)acrylate (G) of the aforementioned epoxy compound The hydroxyl group produced by the reaction of the epoxy group of the compound (g1) with the carboxyl group of the compound (g2) in the molecular structure. The isocyanate group of the hydroxyl group and the diisocyanate compound is reacted under the condition that the number of moles of the hydroxyl group and the number of moles of the isocyanate group are excessive, and the hydroxyl group-containing (meth) acrylate and the residual isocyanate group are further reacted. The poly(meth) acrylate (G') of the obtained epoxy resin can also be used as the compound (A) of the present invention.

The poly(meth)acrylate (E) having a urethane structure and the poly(meth)acrylate (F) of an acrylic polymer as the active energy ray-curable compound (A) are exemplified above. The poly(meth)acrylate (G) of the epoxy resin may be used alone or in combination of two or more. Among these, poly(meth)acrylic acid of an acrylic polymer is preferred because it can simultaneously have a high level of curl resistance and coating film height, and excellent stability when the inorganic fine particles (D) are dispersed. Ester (F).

In the present invention, the hardened coating film can be obtained only by the above-mentioned active energy ray-curable resin (A). However, it is more excellent in curability, can increase the crosslinking density, and can easily obtain a coating film having high hardness, and further From the viewpoint that the viscosity of the slurry can be easily adjusted to a range suitable for dispersion without using a large amount of an organic solvent, it is preferred to use (meth) acrylate (B) in combination, and it is more preferable to use 3 in the molecular structure. ~6 (meth)acrylonitrile groups, and polyfunctional (meth)acrylates having a molecular weight of 100 to 600.

The (meth) acrylate (B) which is generally not easily used as a dispersion medium is contained in combination with the antioxidant (C), and the affinity of the resin (A), the acrylate (B), and the inorganic fine particles (D) Sex becomes very good, showing higher film properties such as hardness or transparency, and can be divided into The dispersion suppresses the generation of the gel, and a composition excellent in storage stability can be obtained.

The polyfunctional (meth) acrylate (B) which can be used in the present invention may, for example, be a compound having one or two (meth) acrylonitrile groups in the molecular structure and having a molecular weight of from 100 to 600 (P1). Or a compound (P2) having a molecular structure of 3 to 6 (meth)acrylonium groups and a molecular weight of more than 600 and less than 3,000.

The compound (P1) having one or two (meth)acrylonium groups in the molecular structure and having a molecular weight of from 100 to 600 may, for example, be 2-hydroxyethyl (meth)acrylate or (methyl). 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, butyl (meth)acrylate, (methyl) Glycidyl acrylate, propylene sulfhydryl Porphyrin, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, benzyl (meth)acrylate, (a) 2-ethoxyethyl acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modification Phosphate (meth) acrylate, phenoxy (meth) acrylate, epoxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, indophenol (A Acrylate, ethylene oxide modified phenol (meth) acrylate, propylene oxide modified phenol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, 2- (Meth) propylene oxiranyl ethyl hydrogen phthalate, 2-(methyl) propylene methoxy propyl hydrogen phthalate, 2-(methyl) propylene methoxy propyl Hexahydrophthalate, 2-(meth)acryloxypropyltetrahydrophthalate, dimethylaminoethyl (meth)acrylate, trifluoro(meth)acrylate Mono(meth)acrylic acid such as ethyl ester, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, and adamantyl mono(meth)acrylate Ester; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, A di(meth)acrylate such as ethoxylated neopentyl glycol di(meth)acrylate or hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate.

The compound (P2) having 3 to 6 (meth)acrylonium groups in the molecular structure and having a molecular weight of more than 600 and less than 3,000 can be, for example, by making 3 to 6 molecules of (meth)acrylofluorene The polyol compound is obtained by adding a polyol compound having a hydroxyl group of a polyol compound having three or more hydroxyl groups in a molecular structure to a polyolefin diol in a range of from 11 to 20 in a repeating unit of polyalkylene oxide. Quality.

The polyol compound having three or more hydroxyl groups in the molecular structure may, for example, be trimethylolethane, trimethylolethane, trimethylolpropane, tetramethylolethane or di-trimethylol. Propane, neopentyl alcohol, dipentaerythritol, and the like. Further, the repeating unit of the polyalkylene oxide is The polyolefin diol in the range of 11 to 20 may, for example, be polyethylene glycol or polypropylene glycol having a repeating unit in the range of 11 to 20.

The (meth) acrylate (B) may be used singly or in combination of two or more. Among these, from the viewpoint of obtaining a coating film having a higher hardness, it is particularly preferably dipentaerythritol hexaacrylate, neopentyltetraol tetraacrylate or trimethylolpropane triacrylate.

In the composition of the present invention, the antioxidant (C) used as an essential component may, for example, be a phenol-based antioxidant, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, or a phosphate-based antioxidant. Wait. These may be used alone or in combination of two or more. Among these, neopentyl alcohol oxime [3-(3,5-di-tertiary butyl-4-) is a hindered phenol-based antioxidant from the viewpoint of less coloration without affecting the appearance of the dispersion. Hydroxybenzene) propionate] or butyl hydroxytoluene (BHT) of a phenolic antioxidant.

[Phenolic antioxidants]

Examples of the phenolic antioxidant include 2,6-di-tertiary butyl-4-ethylphenol and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5. -di-tertiary butylanilino)-1,3,5-three , 2,2-thio-divinyl bis {3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate}, N,N'-hexamethylene double (3,5- Di-tertiary butyl-4-hydroxy-hydrocinnamoguanamine), 3,5-di-tertiary butyl-4-hydroxybenzylphosphonate-diethyl ester, ginseng-(3,5- Di-tertiary butyl-4-hydroxybenzyl)-iso-cyanate, 2,6-di-tertiary butyl phenol, 2,6-di-tri-butyl-p-cresol, 2, 6-di-tertiary butyl-4-methoxyphenol, triethylene glycol-bis{3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate}, 1, 6-hexanediol-bis{3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate}, pentaerythritol-anthracene {3-(3,5-di-three) Grade butyl-4-hydroxyphenyl)propionate}, octadecyl-3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl -2,4,6-paran (3,5-di-tertiary butyl-4-hydroxybenzene)benzene, etc., may be used alone or in combination of two or more.

[Hindered Phenolic Antioxidants]

Examples of the hindered phenol-based antioxidant include 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tertiary butylanilino)-1,3,5. -three , neopentyl alcohol oxime [3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene double (3,5-di-tridecyl) 4-hydroxy-hydrocinnacinamine), 3,5-di-tributyl-4-hydroxybenzylphosphonate-diethyl ester, and ginseng-(3,5-di-tris Butyl-4-hydroxybenzyl)-isocyanate or the like may be used alone or in combination of two or more.

[Hindered Amine Antioxidants]

Examples of the hindered amine-based antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and bis(2,2,6,6-tetramethyl- 4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-butyl-3,5-di-tert-butyl-4-hydroxyl Benzylmalonate, ginseng (2,2,6,6-tetramethyl-4-piperidyl)azinyl triacetate, hydrazine (2,2,6,6-tetramethyl-4 -piperidinyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethyl Piper Ketone), 4-benzylidene-2,2,6,6-tetramethylpiperidine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecyl Amber quinone and the like.

[Organic sulfur-based antioxidants]

The aforementioned organic sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. Examples of such a sulfur-containing antioxidant include di-octadecyl 3-3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearylsulfonate. -3,3'-thiodipropionate, 4,4'-thiobis-3-methyl-6-tertiary butyl phenol , thiodivinyl bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate].

[Phosphate Antioxidant]

As the phosphate ester-based antioxidant, gin [2,4-di-(tris)-butylphenyl]phosphine [2-[[2,4,8,10-肆(1,1-) Dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphino-6-yl]oxy]ethyl]amine, ginseng [2-[(4,6,9) ,11-tetra-tertiary butyldibenzo[d,f][1,3,2]dioxaphosphin-2-yl)oxy]ethyl]amine, ethyl bisphosphite (2, 4-di-tertiary butyl-6-methylphenyl).

Next, the inorganic fine particles (D) used in the present invention will be described.

The inorganic fine particles (D) used in the present invention are not particularly limited, and examples thereof include cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more.

The particle diameter of the inorganic fine particles (D) is preferably in the range of 5 nm to 300 nm in terms of the average primary particle diameter from the viewpoint of obtaining a coating film having higher hardness; more preferably, transparency can be obtained. From the viewpoint of the coating film, it is particularly preferable that the average primary particle diameter is in the range of 5 nm to 150 nm, and the average primary particle diameter is in the range of 5 nm to 50 nm.

Among these, cerium oxide fine particles are preferred from the viewpoint of easy availability and ease of handling. Examples of the cerium oxide fine particles include dry cerium oxide fine particles and wet cerium oxide fine particles. The dry cerium oxide fine particles are, for example, cerium oxide fine particles obtained by burning cerium tetrachloride in an oxygen or hydrogen flame. Further, the wet cerium oxide fine particles are, for example, cerium oxide fine particles obtained by neutralizing sodium citrate with a mineral acid. According to the manufacturing method of the present invention, in the case of using any of the ceria particles, the resulting dispersion The body can maintain dispersion stability well for a long time.

The composition of the present invention contains an active energy ray-curable resin (A), the above-mentioned antioxidant (C), and the above-mentioned inorganic fine particles (D) as essential components. From the viewpoint of obtaining a coating film having a high hardness and obtaining a coating film having a high hardness, the active energy ray-curable resin (A) which is an organic component in the composition, and the acrylate which is used in combination as needed (B) The mass ratio of the inorganic fine particles (D) which is an inorganic component [resin (A) + acrylate (B)] / [inorganic fine particles (D)] is preferably 10 to 90 parts by mass / 90 to 10 parts by mass. The range is particularly preferably in the range of 30 to 90 parts by mass per 70 to 10 parts by mass. Further, from the viewpoint of obtaining a coating film having a higher hardness, it is preferred to use a polyfunctional (meth) acrylate (B) in combination, in which case the active energy ray-curable resin (A) and polyfunctionality ( The mass ratio of the methyl acrylate (B) [resin (A)] / [acrylate (B)] is preferably in the range of 10 to 90 parts by mass / 90 to 10 parts by mass, particularly preferably 10 to 70 parts by mass. /90~30 parts by mass range. Further, the content of the antioxidant (C) is preferably in the range of 0.05 to 0.4% by weight of the inorganic fine particles (D) from the viewpoint of effectively suppressing thickening or gelation.

The composition of the present invention may also contain various additives as needed. Examples of the various additives include a coupling agent (O), a dispersion aid, and the like.

The coupling agent (O) is used for the purpose of improving the dispersibility of the inorganic fine particles (D) by introducing a functional group to the surface of the inorganic fine particles (D). For example, a vinyl-based decane coupling agent, an epoxy-based decane coupling agent, a styrene-based decane coupling agent, a methacryloxy-based decane coupling agent, and an acryloxy-based decane coupling agent may be mentioned. Amine-based decane coupling agent, urea-based decane coupling agent, chloropropyl-based decane coupling A sulfonium coupling agent, a thiol decane coupling agent, an isocyanate decane coupling agent, an aluminum decane coupling agent, or the like.

The vinyl decane coupling agent may, for example, be vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy. Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-benzene Vinyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyl Methyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyl Triethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl. Butylene) propylamine, N-phenyl-3-aminopropyltrimethoxydecane, N-(vinylbenzyl)-2-aminoethyl-3- Hydroxypropyl trimethoxy decane hydrochloride, special amino decane, 3-ureidopropyl triethoxy decane, 3-chloropropyltrimethoxy decane, 3-mercaptopropylmethyldimethoxy Decane, 3-mercaptopropyltrimethoxydecane, bis(triethoxydecylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, allyltrichloromethane, allyltriethyl Oxydecane, allyltrimethoxydecane, diethoxymethylvinylnonane, trichlorovinylnonane, vinyltrichlorodecane, vinyltrimethoxydecane, vinyltriethoxydecane, ethylene Base gin (2-methoxyethoxy) decane.

The epoxy-based decane coupling agent may, for example, be diethoxy(glycidoxypropyl)methylnonane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, or 3-ring. Oxypropoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like.

Examples of the styrene-based decane coupling agent include p-styryltrimethoxydecane.

The methacryloxyloxy decane coupling agent may, for example, be exemplified by 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, and 3 Methyl propylene methoxy propyl methyl diethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane.

Examples of the acryloxy-based decane coupling agent include 3-propenyloxypropyltrimethoxydecane.

The amine-based decane coupling agent may, for example, be N-2(aminoethyl)3-aminopropylmethyldimethoxydecane or N-2(aminoethyl)3-aminopropyl. Trimethoxydecane, N-2 (aminoethyl) 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 3-trimethoxydecyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, and the like.

The urea-based decane coupling agent may, for example, be 3-ureidopropyltriethoxydecane.

The chloropropyl-based decane coupling agent can be exemplified by, for example, 3-chloropropyltrimethoxydecane.

The decane coupling agent of the fluorenyl group, for example, 3-mercaptopropyl propyl Methyl dimethoxy decane, 3-mercaptopropyl trimethoxy decane, and the like.

Examples of the thioether-based decane coupling agent include bis(triethoxydecylpropyl)tetrasulfide.

The isocyanate-based decane coupling agent may, for example, be 3-isocyanatepropyltriethoxydecane.

Examples of the aluminum coupling agent include acetoxy aluminum diisopropylate. These coupling agents may be used alone or in combination of two or more.

The dispersing aid may, for example, be a phosphate compound such as dihydrogen phosphate or triisodecyl phosphite. These may be used alone or in combination of two or more. Among these, isopropyl dihydrogen phosphate excellent in dispersion assisting performance is preferred.

For the composition of the present invention, an organic solvent (T) may also be added as needed. In the dispersion process, the viscosity of the slurry is preferably from 10 to 100 mPa from the viewpoint that the separation of the slurry and the medium is better. The range of s is more preferably 3~60mPa. The scope of s. In order to adjust to such a range, it is preferred to contain an organic solvent (T).

The organic solvent (T) may, for example, be a ketone solvent such as acetone, methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK); or a cyclic ether such as tetrahydrofuran (THF) or dioxolane. Solvent; esters of methyl acetate, ethyl acetate, butyl acetate, etc.; aromatic solvents such as toluene and xylene; carbitol, sirlofur, methanol, isopropanol, butanol, propylene glycol monomethyl ether, etc. Alcohol solvent. These may be used alone or in combination of two or more.

Among these, it is preferred to use and synthesize the aforementioned active energy The solvent used in the line curable resin (A) is the same solvent. Therefore, a ketone solvent is preferred, and methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) are particularly preferred.

The amount of the organic solvent (T) used is preferably such that the viscosity of the slurry becomes 10 to 100 mPa. The way of the s range is adjusted. In the present invention, since the above-mentioned (meth) acrylate (B) which is generally not easily used for dispersion in a wet ball mill can be used as a raw material of a slurry, the organic solvent (T) can be pressed down to less than usual. Usage amount. Specifically, it is preferably used in the range of 30 to 70 parts by mass based on 100 parts by mass of the slurry, and it is preferably from the viewpoint of obtaining a composition having a very high nonvolatile concentration and requiring no concentration step or the like. It is used in the range of 30 to 65 parts by mass.

Next, a method of producing the composition of the present invention will be described.

In the method for producing a dispersion of the present invention, it is preferable to use a stirring tank having a medium filled therein, a rotating shaft, and a rotating shaft coaxial with the rotating shaft, and having the rotation a stirring blade that is rotated by the rotation of the shaft, a supply port of the slurry provided in the agitation tank, a discharge port of the slurry provided in the agitation tank, and a wet seal disposed in a shaft sealing device of the rotating shaft through the agitation tank a ball mill, that is, a wet ball mill having a structure in which the seal portion of the two mechanical seal units is sealed by an external seal liquid, and the supply port is supplied to the agitation tank by the supply port The rotating shaft and the stirring blade are rotated in the stirring tank, and the medium and the slurry are stirred and mixed to pulverize the inorganic fine particles (D) in the slurry. A method in which the inorganic fine particles (D) are dispersed in the active energy ray-curable resin (A) and the (meth) acrylate (B) used in combination, and then discharged from the discharge port. In this case, it is preferred from the viewpoint of suppressing the generation of the gel by adding the antioxidant (C) to the slurry in advance.

Hereinafter, a method of producing a composition using the wet ball mill as described above will be described in detail based on the drawings.

Figs. 1 and 2 show a wet ball mill Y which can be used in the present invention. The wet ball mill Y is characterized by having a shaft sealing device (u1) as shown in Fig. 2. In the wet ball mill Y, the slurry is supplied to the stirring tank (p1) via the supply port (s1) in Fig. 1 . The agitating tank (p1) is filled with a medium, and the slurry is mixed with the medium by agitating blades (r1) that are rotated by the rotation of the rotating shaft (q1) to pulverize the inorganic fine particles (D). The inorganic fine particles (D) are dispersed in the active energy ray-curable resins (A) and (B). The inside of the rotating shaft (q1) is formed with a cavity having an opening on the discharge port (t1) side. A screen type separator 2 as a spacer is provided in the cavity, and a flow path that communicates with the discharge port (t1) is provided inside the separator 2. The slurry in the stirring tank (p1) is pressed by the supply pressure of the slurry, and is transported to the separator 2 on the inner side by the opening of the rotating shaft (q1). The medium having a large particle size cannot pass through the separator 2, and only the slurry having a small particle size can pass therethrough, whereby the medium stays in the stirring tank (p1), and only the slurry is discharged from the discharge port (t1).

The wet ball mill Y has a shaft sealing device (u1) as shown in Fig. 2. The shaft sealing device (u1) has two mechanical sealing units having a rotating ring 3 fixed to the shaft (q1) and a fixing ring 4 fixed to the outer casing 1 of the shaft sealing device of Fig. 1 To form a dense The structure of the sealing portion is arranged, and the arrangement of the rotating ring 3 and the fixing ring 4 in the unit is oriented in the same direction in both units. Here, the sealing portion refers to a pair of sliding surfaces formed by the rotating ring 3 and the fixing ring 4. Further, a liquid sealing space 11 is provided between the two mechanical sealing units, and an external sealing liquid supply port 5 and an external sealing liquid discharge port 6 communicating therewith are provided. In the liquid sealing space 11, the external sealing liquid (R) supplied from the external sealing liquid tank 7 by the pump 8 is supplied through the external sealing liquid supply port 5, and is returned to the external sealing liquid discharge port 6 through the external sealing liquid discharge port 6 The groove 7 is thus circulated and supplied. Thereby, the external sealing liquid (R) is filled in the liquid sealing space 11 in a liquid-tight manner, and in the sealing portion, the gap 9 formed between the rotating ring 3 and the fixing ring 4 is filled with the external sealing liquid (R). ). Lubrication and cooling of the sliding surfaces of the rotating ring 3 and the stationary ring 4 are performed by the sealing liquid (R).

Further, in order to force the fixing ring 4 against the rotating ring 3 by the inflow pressure of the external sealing liquid (R), the force P2 for pressing the fixing ring 4 toward the rotating ring 3 by the spring 10 is sealed by the outside. The inflow pressure of the liquid (R) establishes the balance of the force P3 separating the stationary ring 4 from the rotating ring 3, and sets the inflow pressure of the sealing liquid (R) and the pressure of the spring 10. Thereby, the external sealing liquid (R) is filled in a gap 9 between the fixing ring 4 as the sliding surface and the rotating ring 3, and the active energy ray-curable resins (A) and (B) do not flow into the gap. In the gap 9. When the active energy ray-curable resins (A) and (B) flow into the gap 9, mechanical radicals are generated from the compounds (A) and (B) due to the sliding of the rotating ring 3 and the fixing ring 4 This causes polymerization to gel or thicken, but this risk can be avoided by using a wet ball mill Y having a shaft sealing device such as the aforementioned shaft sealing device (u1).

As the shaft sealing device of the shaft sealing device (u1), for example, a tandem type mechanical sealer or the like can be given. In addition, a commercially available product of the wet ball mill Y having the above-described tandem type mechanical sealer as a shaft sealing device, for example, "LMZ" series manufactured by Ashizawa Finetech Co., Ltd., and the like.

The external sealing liquid (R) is a non-reactive liquid, and examples thereof include various organic solvents as the organic solvent (T). Among these, it is preferably the same as the solvent contained in the component of the slurry to be used, and thus, a ketone solvent, particularly preferably methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) is preferred. .

For example, various kinds of microbeads can be used as the medium filled in the stirring tank (p1) in Fig. 1 . Examples of the material of the microbeads include zirconia, glass, titanium oxide, copper, and zirconia phthalate. Among these, microbeads of zirconia are preferred because of the hardest and less abrasion.

The medium is based on the separation of the medium from the slurry in the screen separator 2 of Fig. 1, and the dispersion time of the inorganic particles is high, so that the dispersion time becomes shorter and the impact on the inorganic particles is not excessive. From the viewpoint of being strong and less likely to cause excessive dispersion of inorganic fine particles, it is preferred that the average particle diameter is in the range of 10 to 1000 μm in terms of the median diameter.

The above-mentioned excessive dispersion phenomenon refers to a phenomenon in which re-agglomeration is caused by the formation of a new active surface by the destruction of inorganic fine particles. When the dispersion occurs, the dispersion gels.

The filling rate of the medium in the stirring tank (p1) in Fig. 1 is preferably from 75 to 90% by volume based on the internal volume of the stirring tank, from the viewpoint of minimizing the power required for dispersion and pulverizing most efficiently. range.

The agitating blade (r1) is touched by the medium and the inorganic particles (D) From the viewpoint of a large impact at the time of collision and an improvement in dispersion efficiency, it is preferable to rotationally drive the peripheral speed of the tip end portion in the range of 5 to 20 m/sec, and more preferably in the range of 8 to 20 m/sec.

The method for producing the wet ball mill Y described above may be a batch type or a continuous type. Moreover, in the case of a continuous type, it may be a circulation type which is supplied again after the slurry is taken out, and may be a non-circulation type. Among these, from the viewpoint of improvement in production efficiency and excellent homogeneity of the obtained dispersion, a cyclic type as shown in Fig. 3 is preferable.

Fig. 3 is a schematic view showing a circulating dispersion cycle using the aforementioned wet ball mill Y. In Fig. 3, the slurry drawn from the storage tank 12 for storing the slurry by the pump 13 is supplied to the agitation vessel (p1) from the supply port (s1) in Fig. 2 . The slurry dispersed in the stirring tank (p1) is returned to the storage tank 12 through the discharge port (t1) through the valve 16 in Fig. 1 . The slurry which has flowed back to the above-mentioned tank 12 is again passed through the aforementioned dispersion path, and the process is repeated to form a cyclic dispersion. The particle size of the slurry was appropriately measured in the middle of the cyclic dispersion, and the dispersion was terminated when the desired value was reached.

When dispersing is carried out using the cyclic dispersion cycle as shown in the above-mentioned Fig. 3, the slurry supply flow rate to the agitation vessel (p1) is equal to the discharge flow rate from the agitation vessel (p1), and the slurry is placed in the agitation vessel ( The residence time in p1) is suitable and the dispersion efficiency is improved. Preferably, the capacity of the stirring tank (p1) per one liter is 30 to 100 L/hr, more preferably 50 to 80 L/hr.

The pump 13 is preferably a diaphragm pump, which is a pump that is less likely to generate mechanical radicals. As an example of a commercially available product, a "TPL" series manufactured by TACMINA Co., Ltd. may be mentioned.

The procedure for supplying the slurry to the agitation tank (p1) is as follows. After filling the medium in the agitating tank (p1) of the wet ball mill Y, the valve 17 connected to the product tank shown in Fig. 3 and the valve 18 as the inlet port of compressed air or nitrogen are closed, and the valve is opened. In the state of 16 and 19, the motor 14 is first operated. The shaft (q1) and the agitation blade (r1) are rotationally driven by the driving of the motor 14. Next, the pump 13 is operated to supply the raw material slurry in the storage tank 12 to the agitation tank (p1) in a predetermined amount by the supply port (s1).

As described above, the procedure for dispersing the inorganic fine particles (D) in the slurry to a desired value and ending the dispersion is as follows:

The pump 13 is stopped, and then the motor 14 is stopped to complete the pulverization. Thereafter, after the valve 19 is closed, the valve 17 is opened and the pump 13 is operated again, whereby the product slurry in the storage tank 12 is transferred into the product tank 15. Next, in order to extract the product slurry remaining in the agitation vessel (p1), the pump 13 is stopped and the valve 17 is closed. Next, the line back to the sump 12 is switched via the valve 16 into communication with the product tank 15. The tank 12 which is evacuated is filled with the same solvent as the solvent contained in the slurry, the motor 14 is operated again, and the pump 13 is operated again, and the product slurry remaining in the agitation tank (p1) is recovered into the product tank. 15 method. At this time, in order to prevent the solvent from being mixed into the product tank 15, the entire amount of the product slurry remaining in the stirring tank (p1) may be stopped before being transferred to the product tank 15, and in order to recover the entire amount of the product slurry to the product tank 15, It may also be stopped at a point in time when the solvent is slightly mixed into the product tank 15.

Figures 4 and 5 relate to a wet ball mill Z that can be used with the present invention. The wet ball mill Z is equipped with a shaft package as shown in Fig. 5. Set (u2) to its characteristics. In the wet ball mill Z, the slurry is supplied into the stirring tank (p2) via the supply port (S2) in Fig. 4 . The stirring tank (p2) is filled with a medium, and the slurry is mixed with the medium by a stirring blade (r2) that is rotated by the rotation of the rotating shaft (q2) to pulverize the inorganic fine particles (D). The inorganic fine particles (D) are dispersed in the active energy ray-curable resins (A) and (B). Further, the separator has an impeller type separator 20 that transmits a medium having a heavy specific gravity to move radially outward while being rotated coaxially with the shaft (q2). The slurry having a light specific gravity is sucked to the axial portion of the separator 35 and discharged from the discharge port (t2).

The wet ball mill Z has a shaft sealing device (u2) as shown in Fig. 5. The shaft sealing device (u2) has two mechanical sealing units having a rotating ring 22 fixed to the shaft (q2) and a fixing to the outer casing 21 fixed to the shaft sealing device in Fig. 5. The ring 23 is disposed in such a manner as to form a sealing portion, and the arrangement of the rotating ring 22 and the fixing ring 23 in the unit faces in opposite directions in both units. Here, the sealing portion refers to a pair of sliding faces formed by the aforementioned rotating ring 22 and the fixing ring 23. Further, there is a liquid sealing space 24 between the two mechanical sealing units, and an external sealing liquid supply port 25 and an external sealing liquid discharge port 26 communicating therewith. The external sealing liquid (R) supplied from the external sealing liquid tank 27 by the pump 28 is supplied to the liquid sealing space 24 via the external sealing liquid supply port 25, and is returned to the aforementioned groove 27 via the external sealing liquid discharge port 26. , thereby circulating supply. Thereby, the sealing liquid (R) is filled in the liquid sealing space 24 in a liquid-tight manner, and at the same time, the gap 29 formed between the rotating ring 22 and the fixing ring 23 in the sealing portion is filled with the external sealing liquid (R). . Lubrication and cooling of the sliding surfaces of the rotating ring 22 and the stationary ring 23 are performed by the sealing liquid (R).

Further, the force P1' for pressing the fixing ring 23 toward the rotating ring 22 by the inflow pressure of the external sealing liquid (R), the force P2' for pressing the fixing ring 23 toward the rotating ring 22 by the spring 41, and the force P2' for pressing the fixing ring 23 toward the rotating ring 22 by the spring 41 are used. The inflow pressure of the sealing liquid (R) establishes the balance of the force P3' separating the stationary ring 23 from the rotating ring 22, and sets the inflow pressure of the sealing liquid (R) and the pressure of the spring 30. Thereby, the sealing liquid (R) is filled in a gap 29 between the fixing ring 22 as the sliding surface and the rotating ring 23 in a liquid-tight manner, and the active energy ray-curable resins (A) and (B) do not flow into the gap. 29 in. When the active energy ray-curable resins (A) and (B) flow into the gap 29, mechanical radicals are generated from the compounds (A) and (B) due to the sliding of the rotating ring 22 and the fixing ring 23. This causes polymerization to gel or thicken, but this risk can be avoided by using a wet ball mill Z having a shaft sealing device such as the aforementioned shaft sealing device (u2).

As the shaft sealing device of the shaft sealing device (u2), for example, a double type mechanical sealer or the like can be given. In addition, a commercially available product of the wet ball mill Z having the above-described double-type mechanical sealer as a shaft sealing device, for example, "MAX NANO GETTER" series manufactured by Ashizawa Finetech Co., Ltd., and "Ultra Apex Mill" manufactured by Shou Industrial Co., Ltd. (UAM) series, "Super Apex Mill (SAM)" series, etc.

The external sealing liquid (R) is a non-reactive liquid, and examples thereof include various organic solvents as the organic solvent (T). Among these, it is preferably the same as the solvent contained in the component of the slurry to be used, and thus, a ketone solvent, particularly preferably methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) is preferred. .

For example, various kinds of microbeads can be used as the medium filled in the stirring tank (p2) in Fig. 4. Examples of the material of the microbeads include zirconia, glass, titanium oxide, copper, and zirconia phthalate. Among these, zirconia beads are preferred because they are the hardest and least wearable, and have a high specific gravity and are well separated from the slurry in the impeller type separator 35.

With respect to the foregoing medium, the separation between the medium and the slurry in the screen separator 20 of Fig. 4 is good, and the dispersion time becomes a shorter time due to the high pulverization ability of the cerium oxide particles, and the cerium oxide particles are added. From the viewpoint that the impact is not excessively strong and the excessive dispersion of the cerium oxide microparticles is unlikely to occur, the average particle diameter is preferably in the range of 10 to 1000 μm in terms of the median diameter.

The filling rate of the medium in the stirring tank (p2) in Fig. 4 is based on the viewpoint that the power required for dispersion is the smallest and can be most efficiently pulverized, preferably from 75 to 90% by volume of the internal volume of the stirring tank. range.

In the agitating blade (r2), when the collision between the medium and the inorganic fine particles (D) is large and the dispersion efficiency is improved, it is preferable to rotationally drive the peripheral speed of the tip end portion to a range of 5 to 20 m/sec. It is in the range of 8~20m/sec.

The manufacturing method using the wet ball mill Z described above may be a batch type or a continuous type. Moreover, in the case of a continuous type, it may be a circulation type which is supplied again after the slurry is taken out, and may be a non-circulation type. Among these, a cycle type as shown in Fig. 6 is preferable from the viewpoint of improvement in production efficiency and excellent homogeneity of the obtained dispersion.

Fig. 6 is a schematic view showing a cyclic dispersion cycle using the aforementioned wet ball mill Z. In Fig. 6, the pump 32 is used to store the slurry from the reservoir 31. The extracted slurry is supplied to the agitation vessel (p2) from the supply port (s2) in Fig. 4 . The slurry dispersed in the stirring tank (p2) passes through the discharge port (t2), and is returned to the storage tank 31 via the valve 35 in Fig. 6 . The slurry which has flowed back to the above-mentioned tank 31 passes through the aforementioned dispersion path again, and the process is repeated to form a cyclic dispersion. The particle size of the slurry was appropriately measured in the middle of the cyclic dispersion, and the dispersion was terminated when the desired value was reached.

When dispersing is carried out using the cyclic dispersion cycle as shown in the above-mentioned Fig. 6, the slurry supply flow rate to the agitation vessel (p2) is equal to the discharge flow rate from the agitation vessel (p2), and the slurry is placed in the agitation vessel ( The residence time in p2) is suitable and the dispersion efficiency is improved. Preferably, the capacity of the stirring tank (p2) per one liter is 30 to 100 L/hr, more preferably 50 to 80 L/hr.

The pump 32 is preferably a diaphragm pump, which is a pump that is less prone to generate mechanical radicals. Examples of commercially available products include the "TPL" series manufactured by TACMINA Co., Ltd., and the like.

The procedure for supplying the slurry to the agitation tank (p2) is as follows. After filling the medium in the agitating tank (p2) of the wet ball mill Z, the valve 36 connected to the product tank shown in Fig. 6 and the valve 37 as the inlet port of compressed air or nitrogen are closed, and the valve is opened. In the state of 35 and 38, the motor 33 is first operated. The shaft (q2) and the agitation blade (r2) are rotationally driven by the driving of the motor 33. Next, the pump 32 is operated to supply the raw material slurry in the storage tank 31 to the agitation tank (p2) in a predetermined amount by the supply port (s2).

As described above, the procedure for dispersing the inorganic fine particles (D) in the slurry to a desired value and ending the dispersion is as follows:

The pump 32 is stopped, and then the motor 33 is stopped to complete the pulverization. Thereafter, after the valve 38 is closed, the valve 36 is opened and the pump 32 is operated again, whereby the product slurry in the sump 31 is transferred into the product tank 34. Next, in order to extract the product slurry remaining in the agitation tank (p2), the pump 32 is stopped and the valve 36 is closed. Next, the line back to the sump 31 is switched via the valve 35 to communicate with the product tank 34. The tank which is evacuated is filled with the same solvent as the solvent contained in the slurry, and the motor 33 is operated again, and the pump 33 is operated again, and the product slurry remaining in the agitation tank (p2) is recovered into the product tank. 34 method. At this time, in order to prevent the solvent from being mixed into the product tank 34, the transfer may be stopped before the entire amount of the product slurry remaining in the stirring tank (p2) is transferred to the product tank 34, and in order to recover the entire amount of the product slurry to the product tank 34, It may also be stopped at a point when the solvent is slightly mixed into the product tank 34.

The wet ball mill Y and the wet ball mill Z are preferably the wet ball mill Y having a screen type separator from the viewpoint of high separation ability between the medium and the slurry.

Further, in the method for producing a composition of the present invention, a large particle having a median diameter of 300 to 1000 μm is used as a medium to carry out a pre-dispersion step, and a median diameter of 15 to 300 μm is used. The smaller particles act as a medium for the formal dispersion step.

In the aforementioned pre-dispersion step, a larger medium having a median diameter of 300 to 1000 μm is used. Since such a medium has a large impact force when it collides with the inorganic fine particles (D), it is suitable for the pulverization of the inorganic fine particles (D) having a large particle size, and is used to pulverize the inorganic fine particles (D) of the raw material to a certain extent. Particle size. In the aforementioned formal dispersion step, it is in use. A medium having a small diameter ranging from 15 to 300 μm. Such a medium has a small impact force when it collides with the inorganic fine particles (D), but the number of particles contained in the same volume increases as compared with a medium having a large particle diameter, and therefore collides with the inorganic fine particles (D). The number of times has increased. Therefore, it is used for the purpose of pulverizing the inorganic fine particles (D) pulverized to a certain extent in the pre-dispersion step into finer particles.

In the method for producing a composition of the present invention, it is preferred to carry out the two stages of the pre-dispersion step and the above-mentioned formal dispersion step in terms of achieving more efficient dispersion. When the pre-dispersion step is too long, the over-dispersion phenomenon may occur. Therefore, the pre-dispersion step is preferably carried out in a range in which the slurry is circulated in the agitation tanks (p1) and (p2) for 1 to 3 cycles.

The composition obtained by the production method of the present invention can be used as a coating material itself, and can be used as an additive with other compounds as needed. Examples of such additives include ultraviolet absorbers, lanthanoid additives, organic beads, fluorine-based additives, rheology control agents, defoaming agents, mold release agents, decane coupling agents, antistatic agents, antifogging agents, and colorants. , organic solvents, inorganic fillers, and the like.

The ultraviolet absorber may, for example, be 2-[4-{(2-hydroxy-3-dodecyloxy)oxy}-2-hydroxybenzene]-4,6-bis(2,4-di) Methylphenyl)-1,3,5-three 2-[4-{(2-Hydroxy-3-dodecyloxy)}}-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-three Three Derivative, 2-(2'-oxaindolecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzene And triazole, 2-oxaindolecarboxy-4-dodecyldiphenyl ketone, 2-o-nitrobenzyloxy-4-dodecyldiphenyl ketone and the like.

Examples of the lanthanoid additive include, for example, dimethyl polyoxy siloxane, methyl phenyl polyoxy siloxane, cyclic dimethyl polyoxy siloxane, methyl hydrogen polyoxy siloxane, polyether modified two. Methyl polyoxyalkylene copolymer, polyester modified dimethyl polyoxyalkylene copolymer, fluorine modified dimethyl polyoxyalkylene copolymer, amine modified dimethyl polyoxyalkylene copolymer, etc. A polyorganosiloxane having an alkyl group or a phenyl group. These may be used alone or in combination of two or more.

Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic acid styrene beads, polyxylene beads, glass beads, acrylic beads, and benzoguanamine resins. Granules, melamine resin particles, polyolefin resin particles, polyester resin particles, polyamide resin particles, polyimide resin particles, polyvinyl fluoride resin particles, polyethylene resin particles, and the like. The average particle diameter of these organic beads is preferably in the range of 1 to 10 μm. These may be used alone or in combination of two or more.

The fluorine-based additive may, for example, be a "MEGAFACE" series of DIC Corporation. These may be used alone or in combination of two or more.

The release agent is, for example, "TEGORad 2200N", "TEGORad 2300", "TEGORad 2100" manufactured by Evonik Degussa Co., Ltd., "UV3500" manufactured by BYK, "Paintad 8526" manufactured by Dow Corning Toray, and "SH-29PA". Wait. These may be used alone or in combination of two or more.

Examples of the decane coupling agent include various decane coupling agents exemplified as the coupling agent (O). These can be used separately It is also possible to use two or more types together.

The antistatic agent may, for example, be a pyridinium, an imidazolium, an anthracene, an ammonium or a lithium salt of bis(trifluoromethanesulfonyl) quinone imine or bis(fluorosulfonyl) quinone imine. These may be used alone or in combination of two or more.

Examples of the organic solvent include various organic solvents and the like which are exemplified as the organic solvent (T). These may be used alone or in combination of two or more.

The amount of the above-mentioned various additives is preferably such a range that the effect of the above-mentioned various additives can be sufficiently exerted without hindering the ultraviolet curing. Specifically, it is preferably 0.01 to 40 parts by mass per 100 parts by mass of the composition of the present invention. The scope.

The coating material comprising the composition of the present invention further contains a photopolymerization initiator (Q). The photopolymerization initiator (Q) may, for example, be diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone or 4,4'-bisdimethylamino group II. Phenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, mischrone, 3,3',4,4'-tetra (three Various diphenyl ketones such as butylperoxycarbonyl)diphenyl ketone; Ketone, oxysulfide 2-methyloxosulfur 2-chlorooxosulfur 2,4-diethyloxysulfide Wait Ketone, oxysulfide Class; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like; alkaloids such as diphenylethylenedione and diacetyl; tetramethyldisulfide a thioether such as methyl mercaptocarbamide or p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid or ethyl 4-dimethylaminobenzoate; 3,3'- Carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2 -methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oxidation of phenylphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine , bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl- 1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy- 2-methylpropan-1-one, 4-benzylidene-4'-methyldimethyl sulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, Benzyl-β-methoxyethyl acetal, methyl phthalyl benzoate, bis(4-dimethylaminophenyl) ketone, p-dimethylamino acetophenone, α, --Dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer 2,4-bis-trichloromethyl-6-[di-(ethoxycarbonylmethyl)amino]phenyl symmetrical three 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl symmetric three 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl symmetric three 蒽醌, 2-tertiary butyl hydrazine, 2-pentyl hydrazine, β-chloropurine, and the like. These may be used alone or in combination of two or more.

Among the above photopolymerization initiators (Q), one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2) -hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1 ,2-diphenylethane-1-one, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)benzene Phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- One or a mixture of two or more of the group of morphylphenyl)-butan-1-one can exhibit activity over a wider range of wavelengths, and a coating having high hardenability can be obtained. good.

The commercially available product of the photopolymerization initiator is, for example, "IRGACURE-184", "IRGACURE-149", "IRGACURE-261", "IRGACURE-369", "IRGACURE-500" manufactured by Ciba Specialty Chemicals Co., Ltd. "IRGACURE-651", "IRGACURE-754", "IRGACURE-784", "IRGACURE-819", "IRGACURE-907", "IRGACURE-1116", "IRGACURE-1664", "IRGACURE-1700", "IRGACURE" -1800", "IRGACURE-1850", "IRGACURE-2959", "IRGACURE-4043", "DAROCUR-1173"; "Lucirin TPO" manufactured by BASF Corporation; "KAYACURE-DETX" manufactured by Nippon Kayaku Co., Ltd., KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA"; "VICURE-10" and "VICURE-55" manufactured by Stauffer Chemical Co., Ltd.; "TRIGONAL P1" manufactured by Akzo Co., Ltd.; "SANDORAY 1000"; "DEAP" manufactured by Apjohn; "QUANTACURE-PDO", "QUANTACURE-ITX", "QUANTACURE-EPD" manufactured by Ward Blenkinsop.

The amount of use of the photopolymerization initiator (Q) is such an amount that the function as a photopolymerization initiator can be sufficiently exhibited, and it is preferable that the precipitation of crystals or the deterioration of the physical properties of the coating film does not occur, specifically Compared It is preferably used in the range of 0.05 to 20 parts by mass based on 100 parts by mass of the coating material, and particularly preferably used in the range of 0.1 to 10 parts by mass.

The coating of the present invention may further be used in combination with the aforementioned photopolymerization initiator (Q) in various photosensitizers. The photosensitizer may, for example, be an amine, a urea, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound or a nitrile or another nitrogen-containing compound.

The coating of the present invention can be used as a coating layer for protecting the surface of a substrate by being applied to various substrates and then being cured by irradiation with an active energy ray. In this case, the coating material of the present invention can be applied directly to the surface protective member, or can be applied to the plastic film (R), and then used as a protective film for a polarizing plate or the like. Alternatively, the coating material of the present invention may be applied to a plastic film (R) to form an optical film which is used as an antireflection film, a diffusion film, and a ruthenium film. Since the coating film obtained by using the coating material of the present invention is characterized by high hardness and low curl, the coating of the present invention is particularly preferably applied to a plastic film (R) for use as a protective film or a film-like molded article.

Here, the plastic film (R) may, for example, comprise polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, cellulose triacetate resin, ABS resin. , plastic film such as AS resin, norbornene resin, cyclic olefin, and polyimide resin.

When the coating material of the present invention is applied to the plastic film (R), the coating amount is preferably in the range of 0.1 to 30 g/m ² , and preferably in the range of 1 to 20 g/m ² . . The film thickness of the coating film of the present invention is 3% or more with respect to the film thickness of the plastic film (R), whereby sufficient hardness as a protective layer can be exhibited. In particular, it is preferable that the film thickness of the coating film is in the range of 3 to 100%, more preferably in the range of 5 to 100%, with respect to the film thickness of the plastic film (R), and particularly preferably with respect to the film-like group. The film thickness of the material is in the range of 5 to 50%.

The coating method of the coating material of the present invention may, for example, be a bar coater coating, Meyer Bar Coating, pneumatic blade coating, gravure coating, reverse gravure coating, lithography. , flexographic printing, screen printing, etc.

The active energy ray which is irradiated when the coating material of the present invention is cured to form a coating film may, for example, be an ultraviolet ray or an electron beam. When it is hardened by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal halide lamp is used as a light source, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. When a high-pressure mercury lamp is used, it is preferable to cure the lamp with a light amount of usually 80 to 160 W/cm in a range of 5 to 50 m/min. On the other hand, when it is hardened by an electron beam, it is preferable to harden it by the electron beam acceleration apparatus which has the acceleration voltage of the range of normally 10-300 kV in the range of 5-50 m/min.

Further, the substrate to which the coating material of the present invention is applied is not only a plastic film (R), but also a surface coating agent for various plastic molded articles such as mobile phones, home electric appliances, automobile bumpers, and the like. In this case, examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.

The coating method is a printing machine that spray-coats the above-mentioned paint or uses a curtain coater, a roll coater, a gravure coater, or the like. The device is applied to a method in which a molded article is used as a top coat and then irradiated with an active energy ray to cure it.

In the transfer method, a transfer material obtained by applying the above-described coating material of the present invention to a substrate sheet having releasability is attached to the surface of the molded article, and then the base sheet is peeled off to transfer the top coat layer to the surface of the molded article. And then irradiating the active energy ray to harden the film; or after the transfer material is attached to the surface of the molded article, irradiating the active energy ray to harden it, and then peeling off the base sheet to transfer the top coat to the surface of the molded article method.

On the other hand, the sheet-following method is followed by a protective sheet having a coating film containing the coating material of the present invention on a substrate sheet, or a protective sheet having a coating film and a decorative layer containing the coating material on the substrate sheet, followed by a plastic sheet. A method of forming a protective layer on the surface of a molded article.

Among these, the coating of the present invention can be preferably used in a transfer method and a sheet-fed method.

In the above transfer method, a transfer material is first formed. The transfer material can be produced, for example, by applying the above-mentioned coating material alone or after mixing with a polyisocyanate compound, and applying it to a substrate sheet, followed by heating to semi-harden (B-stage) the coating film.

Here, the active energy ray-curable resin (A) is a poly(meth)acrylate (F1) and (F2) of an acrylic polymer, or a poly(meth)acrylate (G) of an epoxy resin, or the like. When a compound having a hydroxyl group in the molecular structure is used for the purpose of more efficiently performing the above-described B-staged step, it may be used in combination with a polyisocyanate compound.

If the transfer material is to be manufactured, first, the coating material of the present invention is applied to the substrate sheet. The method of applying the above coating material may, for example, be mentioned A coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a slanting wheel coating method, or the like, a printing method such as a gravure printing method or a screen printing method. The film thickness at the time of coating is preferably such that the thickness of the coating film after curing is 0.5 to 30 μm, preferably 1 to 6 μm, in terms of good abrasion resistance and chemical resistance. The way to apply.

In the above method, after the coating material is applied onto the substrate sheet, the coating film is heat-dried to semi-harden the coating film (B-stage). The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually from 30 seconds to 30 minutes, preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes.

The formation of the surface protective layer of the molded article using the transfer material is carried out, for example, by subjecting the B-staged resin layer of the transfer material to a molded article, followed by irradiation of an active energy ray to cure the resin layer. Specifically, for example, a B-staged resin layer is formed by adhering a B-staged resin layer of the transfer material to the surface of the molded article, and then peeling off the base sheet of the transfer material. After being transferred onto the surface of the molded article, the energy beam is cured by irradiation with an active energy ray to perform cross-linking and hardening of the resin layer (transfer method); or the transfer material is sandwiched in the molding die, A resin is injected into the cavity to fill the resin, and the transfer material is attached to the surface of the resin, and the substrate is peeled off and transferred onto the molded article, and then the energy beam is hardened by irradiation with an active energy ray to carry out the resin. A method of crosslinking hardening of a layer (forming simultaneous transfer method) or the like.

In the sheet-following method, the base sheet of the protective layer-forming sheet prepared in advance and the molded article are bonded to each other, and then the B-staged resin layer is thermally cured by heating. It a method of crosslinking hardening (follow-up method); or sandwiching the protective layer forming sheet into a molding die, and injecting a resin into the cavity to fill it, thereby obtaining a resin molded article and forming a surface thereof and a protective layer After the sheet is followed by heat-hardening by heating, a method of crosslinking and curing the resin layer (forming simultaneous bonding method) or the like is performed.

Next, the coating film of the present invention is a coating film formed by coating the coating material of the present invention on the above-mentioned plastic film (R) to be hardened, or coating the coating material of the present invention as a surface protecting agent for a plastic molded article, A coating film formed by hardening; and the film of the present invention is a laminated film in which a coating film is formed on a plastic film (R).

Among the various uses of the above-mentioned film, such as the above, a film obtained by applying the coating of the present invention to a plastic film (R) and irradiating the active energy ray is used as a polarizing plate for use in a liquid crystal display or a touch panel display. The use of the film is preferred from the viewpoint of excellent hardness of the coating film. Specifically, when the coating material of the present invention is applied onto a protective film of a polarizing plate used in a liquid crystal display or a touch panel display, and the active energy ray is applied to the film, the cured film is made high. A protective film of hardness and high transparency. In the use of the protective film of the polarizing plate, an adhesive layer may be formed on the surface opposite to the coating layer on which the coating of the present invention is applied.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The parts and % in the examples are based on quality unless otherwise stated.

Further, in an embodiment of the invention, the weight average molecule The amount (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220 manufactured by TOSOH Co., Ltd.

Column; protection of TOSOH Co., Ltd .; column H _XL -H + TOSOH Co. Ltd. TSKgel G5000H _XL + TOSOH Co. Ltd. TSKgel G4000H _XL + TOSOH Co. Ltd. TSKgel G3000H _XL + TOSOH TSKgel G2000H Co., Ltd. _XL

Detector; RI (differential refractometer)

Data Processing: SC-8010 manufactured by TOSOH Co., Ltd.

Standard; polystyrene

Sample; tetrahydrofuran solution converted to 0.4% by mass of resin solid content by microfilter (100 μl)

Synthesis Example 1 (Synthesis of acrylic acrylate A1)

500 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as "MIBK") was fed to a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature in the system was raised to 110 while stirring. °C, followed by dropping 2 hours from the dropping funnel containing 250 parts by mass of glycidyl methacrylate, 80 parts by mass of methyl methacrylate, 40 parts by mass of ethyl acrylate, and 5.5 parts by mass of tertiary butyl peroxy- 2-ethylhexanoate The mixture of "PERBUTYL O" manufactured by the emulsifier Co., Ltd. was kept at 110 ° C for 15 hours. Next, after cooling to 90 ° C, 5 parts by mass of p-methoxyphenol and 130 parts by mass of acrylic acid were further fed, and after adding 2.6 parts by mass of triphenylphosphine, the temperature was further raised to 100 ° C for 8 hours to obtain 997 parts by mass of acrylic acid. A solution of methacrylate A1 in methyl isobutyl ketone. The properties of the acrylic acrylate 1 were as follows. Non-volatile content: 50.7 mass%, Gardner viscosity (25 ° C): Z4-Z5, Gardner color number: 1 or less, acid value: 1.5, GPC measured styrene-converted weight average molecular weight ( Mw): 24,000, theoretical propylene sulfhydryl equivalent in terms of solids content: 180 g/eq

Example 1

22.5 parts by mass (22.5 parts by mass of the acrylic acrylate A1 was 11.25 parts by mass) of the methyl isobutyl ketone solution of the acrylic acrylate A1 obtained in the above Synthesis Example 1, and 11.25 parts by mass of dipentaerythritol hexaacrylic acid Ester (hereinafter abbreviated as "DPHA"), 22.5 parts by mass of Aerosil R7200 ("Aerosil R7200" manufactured by Nippon Aerosil Co., Ltd., cerium oxide microparticles having an average primary particle diameter of 12 nm), and 44 parts by mass of MIBK and 0.045 parts by mass of butyl group A hydroxytoluene (hereinafter abbreviated as "BHT") was used to obtain a slurry. The slurry contained 55.25 parts by mass of MIBK in 100 parts by mass.

1000 g of the slurry was used, and the dispersion was carried out using the wet ball mill Z shown in the above-mentioned FIG. 4 [the inner volume: 0.17 L, medium: zirconia beads having a median diameter of 100 μm (filled with 70 with respect to the inner volume of the wet ball mill) The volume %)] is mixed and dispersed by the cyclic dispersion cycle shown in Fig. 6.

First, the slurry is fed into the sump 31 in Fig. 6 to make the horse When the operation is 33, the rotating shaft (q2) and the stirring blade (r2) are rotationally driven, and the power of the motor 33 is adjusted so that the peripheral speed of the front end portion of the agitating blade (r2) becomes 12 m/sec. Next, the slurry was supplied from the supply port (s2) of the slurry of Fig. 4 by the pump 32 so that the flow rate of the slurry was 100 ml/min. The dispersion was obtained by cyclic pulverization for 45 minutes in accordance with the circulation circuit shown in Fig. 6.

1000 g of the obtained dispersion was mixed with 13.5 g of a photoinitiator ("IRGACURE #184" manufactured by Ciba Specialty Chemicals Co., Ltd.) to obtain a coating material. For the coating, the properties were evaluated according to the following various tests, and the results are shown in Table 1.

Coating filtration speed confirmation test

The above coating was filtered using a Kiriyama funnel and 5C filter paper manufactured by Advantech. The faster the filtration rate, the less gel is produced in the step.

Film transparency test

1. Method for preparing hardened coating film

The above coating was applied to a polyethylene terephthalate (PET) film (film thickness: 125 μm) by a bar coater (film thickness: 3 to 4 μm), dried at 70 ° C for 1 minute, and a high pressure mercury lamp was used under nitrogen. The irradiation amount of 500 mJ/cm ² was passed through to harden it, thereby obtaining a test piece having a cured coating film.

2. Transparency test method

The haze value of the coating film was measured using "haze meter HZ-2" manufactured by Suga Test Instruments Co., Ltd. The lower the haze value, the higher the transparency of the coating film.

Storage stability test of paint

Store the above at 40 ° C, 20 ° C, and -20 ° C On the 14th day of the coating, the storage stability under various temperature conditions was tested.

○: No condensate was observed

×: condensate can be seen

Example 2~6

A coating was obtained in the same manner as in Example 1 except that the composition of the composition was the same as that shown in Table 1. The same test as in Example 1 was carried out. The results are shown in Table 1.

Comparative example 1

22.5 parts by mass (22.5 parts by mass of the acrylic acrylate A1 was 11.25 parts by mass) of the methyl isobutyl ketone solution of the acrylic acrylate A1 obtained in the above Synthesis Example 1, and 11.25 parts by mass of dipentaerythritol hexaacrylic acid Ester (hereinafter abbreviated as "DPHA"), 22.5 parts by mass of Aerosil R7200 ( A slurry was obtained by "Aerosil R7200" manufactured by Japan Aerosil Co., Ltd., cerium oxide microparticles having an average primary particle diameter of 12 nm, and 44 parts by mass of MIBK. The slurry contained 55.25 parts by mass of MIBK in 100 parts by mass.

300 g of the slurry was used and dispersed in the same manner as in Example 1 to obtain a dispersion.

1000 g of the obtained dispersion was mixed with 13.5 g of a photoinitiator ("IRGACURE #184" manufactured by Ciba Specialty Chemicals Co., Ltd.) to obtain a coating material. The properties of the coating material were evaluated in the same manner as in the examples, and the results are shown in Table 2.

Comparative example 2~3

A coating material was obtained in the same manner as in Example 1 except that the composition of the composition was the same as that shown in Table 2. The same test as in Example 1 was carried out. The results are shown in Table 2.

Claims (15)

An active energy ray-curable resin composition comprising an active energy ray-curable resin (A), an antioxidant (C), and inorganic fine particles (D). The active energy ray-curable resin composition according to claim 1, wherein the antioxidant (C) is a phenol compound, a hindered phenol compound, a hindered amine compound, an organic sulfur compound or a phosphate compound. The active energy ray-curable resin composition of claim 1, wherein the antioxidant (C) is neopentyl quinone [3-(3,5-di-tertiarybutyl-4-hydroxyphenyl)propionate ], or butyl hydroxytoluene. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the content of the antioxidant (C) is in the range of 0.05 to 0.4% by weight of the inorganic fine particles (D). The active energy ray-curable resin composition according to any one of claims 1 to 4, further comprising (meth) acrylate (B). The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the active energy ray-curable resin (A) is selected from the group consisting of acrylic (meta) acrylate, One or more acrylates in the group of urethane (meth) acrylate and epoxy (meth) acrylate. The active energy ray-curable resin composition of claim 5, wherein the (meth) acrylate (B) is dipentaerythritol hexaacrylate, neopentyltetraol tetraacrylate or trimethylolpropane triacrylate ester. The active energy ray-curable resin composition according to any one of claims 1 to 7, wherein the inorganic fine particles (D) are cerium oxide, zirconium oxide, or oxidation Aluminum particles. The active energy ray-curable resin composition of claim 8, wherein the inorganic fine particles (D) are dry cerium oxide. A method for producing an active energy ray-curable resin composition, characterized in that the inorganic fine particles (D) are dispersed in the active energy ray-curable resin (A) in the presence of an antioxidant (C). The method for producing an active energy ray-curable resin composition according to claim 10, which is carried out by a wet bead mill. A coating material comprising the active energy ray-curable resin composition according to any one of claims 1 to 9. A coating film characterized by hardening a coating material as claimed in claim 12. A laminated film characterized in that a film of the coating of claim 13 is laminated on a plastic film. The laminate film of claim 14, wherein the plastic film is a cycloolefin polymer film.