JP2012167231A - Active energy-ray curing composition, laminated film-shape material, and laminated molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active energy-ray curing composition capable of providing a cured film having high surface hardness and scratch resistance and being rich in stretchability; a laminated film-shaped material obtained by laminating the cured film on the surface of a film-shape material; a laminated molded article obtained by laminating the laminated film-shaped material on the surface of a molded article so that the surface of the laminated film-shape material and the surface of the molded article contact each other; and a laminated molded article obtained by laminating the cured film on the surface of a molded article.SOLUTION: The active energy-ray curing composition contains a specific polyurethane compound (A), a photoinitiator (B), and an inorganic particle (C). The laminated film-shape material is obtained by laminating the cured film. The laminated molded article is obtained by laminating the laminated film-shape material at least on one surface of a molded article, so that the surface of the laminated film-shape material and the surface of the molded article contact each other. The laminated molded article is obtained by laminating the cured film of the active energy-ray curing composition on the surface of a molded article.

Description

  The present invention relates to an active energy ray-curable composition, a laminated film-like product, and a laminated molded product.

  Conventionally, cases such as mobile phones and personal computers have been decorated by molding or painting with a spray after molding using a thermoplastic resin kneaded with pigment or the like. However, with these existing methods, it has become difficult to meet the recent market demands for various design properties, so the transfer foil method, insert molding method, in-mold molding method can be used to decorate molded products. The injection molding simultaneous decorating method such as is often used.

  The injection molding simultaneous decorating method is, for example, an insert molding method, in which a decorative film-like material pre-printed with a design or the like is vacuum-molded and inserted into a mold, and then a thermoplastic resin is melt-injected into the mold. This is a decoration method that has been used mainly for small automotive parts and the like.

  In such a decorative molded product, for the purpose of imparting scratch resistance, the above-mentioned decorative film-like product may be provided with a cured film layer having a hard coat performance. . However, in order to decorate a larger molded product using such a decorative film-like material, cracks or the like do not occur even if the cured film layer is molded into various shapes in addition to high surface hardness. Stretchability is required.

  As a material for the cured film layer, Patent Document 1 proposes an active energy ray-curable composition containing a polyurethane compound obtained from an epoxy (meth) acrylate having two hydroxyl groups in a molecule and a diisocyanate compound. However, when the active energy ray-curable composition of Patent Document 1 is used for decoration of a molded product larger than the conventional one such as a case of a personal computer, the cured product of the obtained active energy ray-curable composition is used. There may be cases where the stretchability is not sufficient, and further, a stretchable material is desired.

JP 2003-212938 A

  The present invention relates to an active energy ray-curable composition having a high surface hardness and scratch resistance and capable of obtaining a cured film having excellent stretchability, and a laminated film-like material in which the cured film is laminated on the surface of the film-like material , Providing a laminated molded product in which the laminated film is laminated on the surface of the molded product so that the surface of the film and the surface of the molded product are in contact with each other, and a laminated molded product in which the cured film is laminated on the surface of the molded product The purpose is to do.

The gist of the present invention is that a polyurethane compound (A) (hereinafter referred to as “component (A)”) obtained by reacting the following components (a1), (a2) and (a3), a photopolymerization initiator: An active energy ray-curable composition (hereinafter referred to as “the present composition”) containing (B) (hereinafter referred to as “component (B)”) and inorganic particles (C) (hereinafter referred to as “component (C)”). ) Is the first invention.
(A1) component: diol having a ring structure in the molecule and a number average molecular weight (Mn) of 50 to 500 (a2) component: diisocyanate (a3) component: one hydroxyl group and one or more photopolymerizable molecules in the molecule Compound having a group

  Further, the gist of the present invention is that a laminated film-like product (hereinafter referred to as “the present laminated film-like material”) in which a cured film (hereinafter referred to as “the present cured film”) of the present composition is laminated on the surface of the film-like material. Is referred to as a second invention.

  Furthermore, the gist of the present invention is that a laminated molded product (hereinafter referred to as “the present film-like product”) is laminated such that the surface of the molded product and the surface of the molded product are in contact with the surface of the molded product. The third invention is referred to as “laminated molded product”.

  The gist of the present invention is a fourth aspect of a laminated molded product in which a main cured film is laminated on the surface of the molded product (hereinafter referred to as a “main cured film laminated molded product”).

  Since this composition has a high surface hardness and scratch resistance and is capable of obtaining a cured film rich in stretchability, it is suitable for simultaneous injection molding of medium-sized or larger molded products such as personal computer housings. It is.

Component (a1) The component (a1) used in the present invention is a component for obtaining the component (A) described later, and is a diol having a ring structure in the molecule of 50 to 500, preferably 100 to 400. . In the present invention, Mn of the component (a1) represents a number average molecular weight calculated from the structural formula.

  By setting the Mn of the component (a1) to 50 to 500, the surface hardness and stretchability of the cured film can be improved. By making the Mn of the component (a1) 500 or less, the reactivity with the component (a2) can be improved, and the obtained component (A) can be a high molecular weight product. It can be made excellent in stretchability.

  Examples of the component (a1) include aromatic glycols and alicyclic glycols. Of these, alicyclic glycols are preferred in terms of the weather resistance of the cured film.

  Specific examples of the aromatic glycol include bisphenol A, bisphenol F, resorcin and hydroquinone. These can be used alone or in combination of two or more.

  Specific examples of the alicyclic glycol include hydrogenated bisphenol A, hydrogenated bisphenol F, cyclopentanediol, cyclopentanedimethanol, cyclohexanediol, cyclohexanedimethanol, norbornanediol, norbornanedimethanol, decalindiol, decalindimethanol, Examples include tricyclodecane diol and tricyclodecane dimethanol. These can be used alone or in combination of two or more. Among these, hydrogenated bisphenol A, cyclopentane dimethanol and tricyclodecane dimethanol are preferable in terms of the surface hardness of the cured film.

Component (a2) The component (a2) used in the present invention is a diisocyanate for obtaining the component (A).

  Examples of the component (a2) include aromatic diisocyanates such as 2,4-diphenylmethane diisocyanate; aliphatic diisocyanates; alicyclic diisocyanates such as dicyclohexylmethane-4,4-diisocyanate; araliphatic diisocyanates such as xylene diisocyanate; and These burette bodies or allophanate bodies are mentioned. These can be used alone or in combination of two or more. Among these, an alicyclic polyisocyanate and an aliphatic diisocyanate are preferable, and an aliphatic diisocyanate is more preferable in that a main cured film having no color can be obtained.

  Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate. Among these, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate are preferable from the viewpoint of curability of the component (A) to be obtained.

Component (a3) The component (a3) used in the present invention is a component for introducing a photopolymerizable group into the component (A), and has one hydroxyl group and one or more photopolymerizable groups in the molecule. It is a compound that has.

  As the component (a3), for example, mono (meth) acrylate having a hydroxyl group or an alkylene oxide adduct thereof; monohydroxy poly (meth) acrylate or an alkylene oxide adduct thereof; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl methacrylate An addition reaction product of a monoepoxy compound such as polyethylene glycol and (meth) acrylic acid; an addition reaction product of polyalkylene glycol such as polyethylene glycol and mono (meth) acrylic acid; and a mono product of polycaprolactone diol (n = 1 to 5) (Meth) acrylate is mentioned. These can be used alone or in combination of two or more. Among these, mono (meth) acrylate and monohydroxy poly (meth) acrylate having a hydroxyl group are preferable in terms of the surface hardness of the cured film. In the present invention, “(meth) acryl” means “acryl” or “methacryl”.

  Specific examples of the mono (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

  Specific examples of monohydroxy poly (meth) acrylate include pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Among the mono (meth) acrylate and monohydroxypoly (meth) acrylate having a hydroxyl group, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferable in terms of surface hardness and stretchability of the cured film.

Component (A) Component (A) used in the present invention is a component for imparting excellent surface hardness and stretchability to the cured film, and the components (a1), (a2) and (a3) described above. Is a polyurethane compound obtained by reacting

  The method for synthesizing the component (A) is not particularly limited, and various known urethane (meth) acrylate synthesis methods can be employed. As a method for synthesizing the component (A), for example, the component (a2) and then the component (a3) are sequentially added dropwise to a mixture of the component (a1) and the polyurethane-forming catalyst at 50 to 90 ° C. (A ) To obtain the component.

  Examples of the polyurethane forming catalyst include amine-based catalysts and organometallic catalysts. Specific examples of the amine catalyst include triethylamine, N, N-dimethylcyclohexylamine and dimethanolamine. These can be used alone or in combination of two or more. Specific examples of organometallic catalysts include stannous octoate, stannous laurate, di-n-butyltin dilaurate, di-n-butyltin dimaleate, di-n-butyltin diacetate, and di-n-octyl. Organic tin compounds such as tin diacetate can be mentioned. These can be used alone or in combination of two or more. Among these, an organometallic catalyst is preferable and di-n-butyltin dilaurate is more preferable because a high catalytic effect can be obtained with a small amount.

  In the present invention, when obtaining the component (A), it is necessary for the purpose of facilitating temperature control during the synthesis of the component (A) and improving the workability by reducing the viscosity of the obtained component (A). Accordingly, at least one selected from the components (a1) to (a3) can be diluted with the diluent solvent for component (A) and used.

  Examples of the diluent solvent for component (A) include aromatic solvents such as toluene and xylene; cyclic hydrocarbon solvents such as cyclohexane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and ethyl acetate and n-butyl acetate. Acetate solvent These can be used alone or in combination of two or more.

  The end point of the reaction for obtaining the component (A) can be confirmed by the residual amount of isocyanate groups in the obtained component (A). (A) As a residual amount of the isocyanate group in a component, 0.05 mol% or less is preferable and 0.01 mol% or less is more preferable. In the present invention, the residual amount of isocyanate groups indicates a value obtained by quantification by a back titration method using an amine and hydrochloric acid. A specific method for quantifying isocyanate groups is as follows.

The obtained component (A) (W [g]) is dissolved in 25 ml of a solvent such as chlorobenzene and further mixed with 25 ml of a 0.1N di-n-butylamine chlorobenzene solution. After adding 1 to 2 drops of a commercially available indicator such as bromophenol blue to the obtained mixed solution, titration is performed with a commercially available 0.1N hydrochloric acid ethanol solution. When the color changes from blue-violet to yellow, the end point is taken and the dripping amount (Y [ml]) is read. The same operation is performed without the component (A), and the amount of blank dripping (X [ml]) is obtained. The residual amount of isocyanate groups is calculated using the following formula.
(Remaining amount of isocyanate group [%]) = (Y−X) × F × 0.42 / W
Y: Amount of dropwise addition of 0.1N hydrochloric acid ethanol solution (ml) for the sample of component (A) obtained
X: Amount of 0.1N hydrochloric acid ethanol solution dropped in the blank [ml]
F: Factor value of 0.1N hydrochloric acid ethanol solution W: Mass of component (A) [g]

  The weight average molecular weight (Mw) of the component (A) is preferably 1,000 to 100,000, more preferably 1,500 to 30,000. When the Mw of the component (A) is 1,000 to 100,000, the component (A) can be stably produced without gelation, the workability of the component (A), and the main curing obtained. It is preferable in terms of stretchability of the film. In addition, in this invention, Mw of (A) component adjusts the tetrahydrofuran solution (0.4 mass%) of this composition, Tosoh Co., Ltd. column (TSK gel super HZM-M and TSK guard column super HZ) 100 μl of the above solution was injected into a gel permeation chromatography apparatus (HLC-8320GPC EcoSEC, trade name) manufactured by Tosoh Corporation equipped with -L, trade name), flow rate of 1 ml / min, eluent tetrahydrofuran and column temperature. It is a value measured under the condition of 40 ° C. and converted with standard polystyrene.

Mw of (A) component can be adjusted with the molar ratio of (a1) component, (a2) component, and (a3) component. The molar ratio of the component (a1), the component (a2) and the component (a3) is preferably 0.8 <M <1.2 in the following formula.
M = (m ₁ × 2 + m ₃ ) / m ₂ × 2
_However, m 1, _{m 2} and _{m 3} are each component (a1) shows the component (a2) and (a3) the molar amounts of components _{a m} 1 ₌ m 2 -1.
By setting M within the above range, preferably M = 1, the viscosity of component (A) can be lowered, and the surface hardness and stretchability of the cured film tend to be improved.

Component (B) Component (B) is a polymerization initiator for efficiently curing the composition with active energy rays. Examples of the component (B) include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, and acylphosphine oxide compounds. These can be used alone or in combination of two or more. Component (B) is 2-hydroxy-2-methyl-1-phenylpropan-1-one in that the curability of the composition is improved and a cured film having excellent surface hardness and scratch resistance is obtained. 1-hydroxycyclohexyl-phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl At least one photoinitiator selected from] -2-morpholinopropan-1-one is preferred.

Component (C) Component (C) is a particle for imparting scratch resistance to the cured film. Examples of the component (C) include silica, zirconia, alumina, and zinc oxide. In the present invention, the component (C) is preferably inorganic particles modified with an organic compound. A commercially available thing can be used as an inorganic particle modified | denatured with the organic compound. As the inorganic particles, inorganic fine particles having an average primary particle diameter of 300 nm or less are preferable.

  Examples of inorganic particles modified with an organic compound include condensation of inorganic fine particles (hereinafter referred to as “(c1) component”) and a hydrolysis product of an organic silane compound (hereinafter referred to as “(c2) component”). Organic-inorganic fine particles obtained by the above. Moreover, you may use a commercially available thing as (c1) component.

  Examples of the component (c1) include those having an average primary particle diameter of 1 to 300 nm, preferably 5 to 80 nm and dispersed in a colloidal state in a dispersion medium such as water or an organic solvent. The average primary particle diameter of the component (c1) is preferably 1 nm or more in terms of not causing gelation during the reaction with the component (c2), and preferably 300 nm or less in terms of transparency of the cured film. As the component (c1), silica is preferable from the viewpoint of scratch resistance of the cured film. In the present invention, the average primary particle diameter of the component (c1) is a value determined by a gas adsorption method (specific surface area equivalent diameter determined by the BET method).

  Examples of the component (c2) include hydrolysis products of silane coupling agents represented by the following formulas (1) and (2). These can be used alone or in combination of two or more.

(In the formula (1) and formula (2), X (meth) acryloyloxy group, a vinyl phenylene group, a vinyl group, a glycidyl group, an amino group, a mercapto group or an isocyanate group. Further, R ¹ is C 1 -C Represents a linear or branched alkylene group of ˜8, R ² and R ³ represent a linear or branched alkyl group having 1 to 8 carbon atoms, m is a positive integer of 1 to 3, and n is 0. A positive integer of ˜2, m + n represents a positive integer of 1 to 3)

  As the component (c2), in addition to the above compound, for example, a silane compound obtained by adding (meth) acrylic acid to the epoxy group or glycidyl group of the hydrolysis product of the silane coupling agent represented by the formula (1), amino A silane compound obtained by Michael addition of a compound having two (meth) acryloyloxy groups to the group, a silane compound obtained by adding a compound having a (meth) acryloyloxy group and an isocyanate group to an amino group or a mercapto group, and (meth) to the isocyanate group The hydrolysis product of the silane compound which added the compound which has an acryloyloxy group and a hydroxyl group is mentioned.

  As the component (c2), a silane compound having a (meth) acryloyloxy group, a vinylphenylene group or a vinyl group is preferable. By using these silane compounds, a fully cured film having excellent scratch resistance can be obtained. Specific examples of preferable component (c2) include 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- ( Mention may be made of (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, vinylphenylenetrimethoxysilane, vinylphenylenetriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane. Among these, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are more preferable because they are excellent in polymerization activity due to active energy ray irradiation.

  As a method for producing the component (C), for example, after obtaining a mixture of the component dispersion (c1) and the component (c2) in which the component (c1) is dispersed in a dispersion medium, the dispersion medium of the component (c1) is used. Under normal pressure or reduced pressure, azeotropic distillation is performed together with a medium having a polarity lower than that of the component (c1) dispersion medium to replace the component (c1) dispersion medium with a medium having a lower polarity. (C2) The method of condensing a component is mentioned. Specific examples of detailed conditions of the method for producing the component (C) are shown below.

  (C1) As a method for preparing the mixture of the component dispersion and the component (c2), (c1) a method of mixing the component dispersion and the component (c2), or (c1) a method of mixing the component dispersion, the organosilane compound, and water A method of hydrolyzing an organosilane compound in a state where it is mixed with a decomposition catalyst to obtain a component (c2) can be mentioned.

  As a method for obtaining the component (c2) by hydrolyzing the organic silane compound, for example, 0.5 mol as a hydrolysis catalyst with respect to 1 mol of the organic silane compound in the presence or absence of an organic solvent such as an alcohol solvent. Examples include a method in which ˜6 mol of water or 0.001 to 0.1 N hydrochloric acid or acetic acid aqueous solution is added and then the alcohol produced by hydrolysis is removed from the system while stirring under heating.

  In the above production method, the mixing ratio of the component (c1) and the component (c2) is 5% when the total of the component (c1) and the component (c2) is 100% by mass. -90 mass% is preferable, and 20-80 mass% is more preferable. When the content of the component (c1) is 5% by mass or more, there is a tendency that a fully cured film having excellent scratch resistance can be obtained. In addition, when the content of the component (c1) is 90% by mass or less, the dispersion stability of the component (C) in the composition is good, and a cured film having excellent stretchability tends to be obtained.

  In the condensation reaction of the component (c1) and the component (c2), first, the dispersion medium of the component (c1) and the water generated by the condensation reaction are heated at 60 to 100 ° C., preferably 70 to 90 ° C. under normal pressure or reduced pressure. The azeotropic distillation is performed under the conditions, and the solid content concentration of the reaction liquid of the component (c1) and the component (c2) is set to 50 to 90% by mass.

  Next, after adding a solvent having a lower polarity than the dispersion medium of the component (c1) to the reaction liquid of the component (c1) and the component (c2), a solvent having a low polarity, water, and the dispersion medium of the component (c1) While further azeotropically distilling at 150 ° C., preferably 80 to 130 ° C., the solid content concentration of the reaction liquid of component (c1) and component (c2) is maintained at 30 to 90% by mass, preferably 50 to 80% by mass, and 0 The condensation reaction is carried out with stirring for 5 to 10 hours to obtain component (C). At this time, for the purpose of promoting the condensation reaction, a catalyst such as water, acid, base, salt or the like may be used in the reaction solution of the component (c1) and the component (c2).

This composition This composition contains (A) component, (B) component, and (C) component. In the present invention, for the purpose of imparting surface hardness to the cured film, (meth) acrylate (D) other than the component (A) (hereinafter referred to as “component (D)”) as necessary in the composition. Can be blended.

  Examples of the component (D) include mono (meth) acrylate, di (meth) acrylate, trifunctional or higher polyfunctional (meth) acrylate, epoxy poly (meth) acrylate, urethane poly (meth) acrylate, and polyester poly (meth). ) Acrylates.

  Specific examples of mono (meth) acrylates include alkyl mono (meth) acrylates having a linear, branched or ring structure having 1 to 20 carbon atoms; and linear, branched or ring structures having 1 to 20 carbon atoms. Examples thereof include hydroxyalkyl mono (meth) acrylates.

  Specific examples of di (meth) acrylate include linear, branched or ring structures such as 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanediol di (meth) acrylate, etc. Di (meth) acrylates of alkane diols having the above and alkylene oxide adducts thereof; and polyether diol di (meth) acrylates such as polyethylene glycol (repeat unit n = 2 to 15) di (meth) acrylate.

  Specific examples of trifunctional or higher polyfunctional (meth) acrylates include (meth) acrylic acid modified products of polyhydric alcohols such as trimethylolpropane, pentaerythritol, and glycerin, or alkylene oxide modified products thereof; and tris (2-hydroxy (Meth) acrylic acid modified product of ethyl) isocyanurate or alkylene oxide modified product thereof.

  Specific examples of the epoxy poly (meth) acrylate include bisphenol type epoxy di (meth) acrylate obtained by reacting a bisphenol type epoxy resin obtained by a condensation reaction of bisphenol A and epichlorohydrin with (meth) acrylic acid.

  Specific examples of the urethane poly (meth) acrylate include a hydroxy group-containing (meth) acrylate having at least one organic isocyanate compound, one or more (meth) acryloyloxy groups and one hydroxy group in the molecule, and Examples include those obtained by reacting at least one diol selected from alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, and amide diol as necessary.

  Specific examples of the polyester poly (meth) acrylate include those obtained by a reaction between a polybasic acid such as phthalic acid, a polyhydric alcohol such as ethylene glycol, and (meth) acrylic acid.

  (D) component can be used individually or in combination of 2 or more types.

  The component (D) is preferably a trifunctional or higher polyfunctional (meth) acrylate in terms of the surface hardness of the cured film.

  Specific examples of preferable trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth). Examples include acrylate, pentaerythritol tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate.

  The trifunctional or higher polyfunctional (meth) acrylate is at least selected from dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. One type is more preferable.

  As a compounding quantity of (A) component in this composition, 10-95 mass% is preferable in the total amount of (A) component, (C) component, and (D) component, and 20-90 mass% is more preferable. . (A) This composition which is excellent in workability | operativity with the compounding quantity of 10-95 mass% is obtained, and exists in the tendency which can obtain the main cured film excellent in surface hardness and a drawability.

  As a compounding quantity of (B) component in this composition, 0.01-50 mass parts is preferable with respect to 100 mass parts of total amounts of (A) component, (C) component, and (D) component, and 0. 1-30 mass parts is more preferable. When the blending amount of the component (B) is 0.01 to 50 parts by mass, the curability of the present composition becomes good, and there is a tendency that a fully cured film excellent in surface hardness and scratch resistance can be obtained.

  As a compounding quantity of (C) component in this composition, 5-90 mass% is preferable in the total amount of (A) component, (C) component, and (D) component, and 10-80 mass% is more preferable. . (C) It exists in the tendency which can obtain the main cured film which is excellent in transparency, surface hardness, abrasion resistance, and a drawability with the compounding quantity of 5-90 mass%.

  As a compounding quantity of (D) component in this composition, 0-50 mass% is preferable in the total amount of (A) component, (C) component, and (D) component, and 5-40 mass% is more preferable. . (D) It exists in the tendency which can obtain this hardened | cured film which is excellent in surface hardness and a drawability with the compounding quantity of 50 mass% or less.

  A polymerization inhibitor can be blended in the composition as necessary. Examples of the polymerization inhibitor include nitroso polymerization inhibitors such as nitrosophenylhydroxylamine ammonium salt; quinone polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether and benzoquinone; N, N-diphenylpicrylhydrazyl (DPPH), And radical scavengers such as triphenylmethyl; and benzotriazole antioxidants. These can be used alone or in combination of two or more.

  In addition, the composition contains a non-reactive thermoplastic polymer compound, a rheology modifier such as an organic benton, polyamide, microgel, and a fibrous resin, a surface modifier represented by silicone, and an ultraviolet absorber. Various additives such as a light stabilizer, an antioxidant, a polymerization inhibitor, a silane coupling agent, an organic filler, and an anti-sagging agent can be blended.

  Furthermore, an inorganic filler other than the component (C) can be blended with the present composition as necessary for the purpose of imparting shape stability, heat resistance or slipperiness, or improving conductivity. A known method can be used as a blending method of the inorganic filler.

  As an inorganic filler, for the purpose of obtaining a cured film having excellent shape stability, heat resistance, and slipperiness, for example, a metal oxide such as silica, alumina, titanium oxide or a composite oxide thereof, a metal oxide thereof Examples thereof include surface-treated metal oxides or surface-treated composite oxides obtained by coating a product or composite oxide with a silane coupling agent or the like, and hydroxides such as aluminum hydroxide, magnesium hydroxide, and potassium hydroxide. In addition, as the inorganic filler, for the purpose of improving the conductivity of the cured film, for example, metal particles such as gold, silver, copper, nickel or alloys thereof, carbon, carbon nanotube, carbon nanohorn, fullerene, etc. Examples thereof include particles and particles of glass, ceramics, plastics, metal oxides and the like coated with metal or ITO (indium tin oxide). The conductive particles preferably have an aspect ratio of 5 or more in terms of conductivity. In the present invention, the aspect ratio is determined by (major axis) / (minor axis).

  The particle diameter of the inorganic filler is preferably 1 μm or less in terms of area average particle diameter from the viewpoint of the optical performance of the present composition.

  The compounding quantity of an inorganic filler can be adjusted according to the use for which this composition is used, required mechanical strength, fluidity | liquidity, etc.

  In the present invention, when the composition is applied to the surface of a substrate such as a film-like product or a molded product, which will be described later, the viscosity of the composition is adjusted according to the application method. The composition can be diluted with an organic solvent. Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ether solvents such as propylene glycol monomethyl ether, and the same diluent solvents for component (A). The blending amount of the organic solvent in the present composition is preferably from the viewpoint of coating workability so that the amount of the curable component in the present composition is 20% by mass or more of the final composition when coating. For example, when spraying the composition, the Ford Cup No. It is preferable to add an organic solvent using a 4 viscometer so that the viscosity is about 15 to 60 seconds at 20 ° C.

Film-like product In the present invention, the present laminated film-like product can be obtained by laminating the present cured film on the surface of the film-like product.

  Examples of the resin forming the film-like material include cellulose resin, polyester resin, methacrylic resin, polycarbonate resin, polystyrene resin, crystalline polyolefin resin, amorphous polyolefin resin, polyether sulfone resin, acrylonitrile-styrene copolymer resin, Examples include polyamide resins, polyarylate resins, and polymethacrylimide resins. Resins that form film-like materials contain various additives such as antioxidants, light stabilizers, UV absorbers, fluorescent brighteners, transesterification agents, and antistatic agents depending on the purpose. Can be used.

  As a film-like thing, what provided the pattern, the easily bonding layer, or the release layer on the surface according to the objective can be used. The thickness of the film-like material is preferably 0.05 to 1 mm in terms of the surface hardness of the laminated film-like material described later.

Main cured film The main cured film is a film obtained by applying the composition to the surface of a substrate such as a film and then curing the composition with active energy rays. As thickness of this hardened film, 0.001-0.1 mm is preferable at the point of sclerosis | hardenability of this composition and the surface hardness of this hardened film.

  As a method of applying this composition to the surface of a substrate such as a film-like material, a bar coater coating method, a Mayer bar coating method, an air knife coating method, a gravure coating method, a reverse gravure coating method, a micro gravure coating method, a brush coating Method, spray coating method, shower flow coating method, dip coating method, curtain coating method, offset printing method, flexographic printing method, screen printing method and potting method.

Examples of active energy rays for curing the present composition applied to the surface of a substrate such as a film-like material include α, β, γ rays, ultraviolet rays, and the like. preferable. Examples of the ultraviolet ray generation source include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless UV lamp using a magnetron, and an LED. The atmosphere for curing the present composition may be air, an inert gas such as nitrogen or argon, but an air atmosphere is preferred in terms of practicality and economy. Examples of the curing conditions for the present composition include irradiation conditions of 300 mJ / cm ² in terms of the integrated light amount using a high-pressure mercury lamp when ultraviolet rays are used as the active energy ray.

The present laminated film- like product is obtained by laminating the present cured film on one surface of the film-like product. The present laminated film-like product is suitable for a hard coat film since a main cured film having excellent surface hardness is laminated on one surface. In addition, the present laminated film-like product is suitable for a film for in-mold decoration during injection molding because a cured film excellent in stretchability is laminated on one surface.

  When this laminated film-like product is used as a film for in-mold decoration at the time of injection molding, the resin of the film-like product is preferably a polyester resin, a methacrylic resin or a polycarbonate resin. Moreover, when using this laminated film-like material as a film for in-mold decoration during injection molding, the thickness of the film-like material is preferably 0.05 to 1 mm in terms of the surface hardness of the laminated film-like material. In view of the moldability of the laminated film, 0.05 to 0.2 mm is preferable. When this laminated film is used as an in-mold decorative film during injection molding, the thickness of the cured film is 0.001 in terms of the curability of the composition and the surface hardness of the laminated film. ˜0.1 mm is preferable, and 0.001 to 0.01 mm is preferable from the viewpoint of the moldability of the laminated film.

  Incidentally, in the present invention, in-mold decoration at the time of injection molding, in the case of injection molding of plastic or the like, by first mounting a film having a hard coat layer and a printing layer on the mold surface, then injection molding, A technique for decorating the surface of a molded product with a hard coat layer or printed layer in a mold. In the present invention, examples of the in-mold decoration at the time of injection molding include an insert molding method, an in-mold lamination method, and an in-mold decoration method.

Molded product In the present invention, the present film-shaped product laminated molded product can be obtained by laminating the present laminated film-shaped product on the surface of the molded product. Examples of the resin for forming a molded article include a polycarbonate resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), and a polymer alloy containing the polycarbonate resin. In the present invention, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, a plasticizer, a stabilizer, a release agent, an antistatic agent, a colorant, a difficult agent, and a resin are formed as necessary. Various additives such as a flame retardant, glass fiber, carbon fiber, and anti-drip agent can be blended.

In the present invention, in the present invention, the present laminated film product is laminated on the surface of the molded product so that the surface of the film product and the surface of the molded product are in contact with each other to obtain the present laminated film product. Can do. As a manufacturing method of this film-form laminated molded product, for example, a method obtained by an in-mold decoration method at the time of injection molding can be mentioned.

  A thermoplastic resin that can be melt-integrated with the film-like material is preferable as the resin that forms the molded product when the film-like product laminated molded product is obtained by the in-mold decoration method during injection molding. Examples of the thermoplastic resin that can be melted and integrated with the film-like material include a polymer alloy including a polycarbonate resin, an ABS resin, and a polycarbonate resin. In the present invention, when a molded product having poor adhesion to the film-like product is used, an adhesive layer can be formed between the film-like product and the molded product.

  In this invention, a printing layer etc. can be provided in the surface of the film-like thing of this laminated | multilayer film-like thing. In this case, when using a molded product having poor adhesion to the printed layer, an adhesive layer can be formed between the printed surface of the film-like product and the molded product.

Main cured film laminate molded product In the present invention, a final cured film laminate molded product in which a main cured film is laminated on the surface of a molded product can be obtained. As a manufacturing method of the present cured film laminated molded product, for example, a method of applying the present composition directly to the surface of the molded product and then curing with active energy rays to laminate the cured film on the surface of the molded product and at the time of injection molding The method obtained by peeling a film-like substance after forming this film-form laminated molded article by the in-mold decoration method is mentioned.

  When the final cured film laminate molded product is obtained by applying the composition directly on the surface of the molded product and then curing with active energy rays to laminate the final cured film on the surface of the molded product, the final cured film laminate molding Examples of the method for producing the product include the same method as the method for applying the present composition for obtaining the cured film to the surface of a substrate such as a film.

  A resin that forms a film-like product when it is obtained by peeling off the film-like product after forming this film-like product laminate-molded product by an in-mold decoration method during injection molding As such, it is preferable to use a film that easily peels the film-like material from the main cured film of the laminated film-like material. In the present invention, a release layer can be formed between the film-like material and the main cured film in order to facilitate the peeling of the film-like material from the main cured film of the laminated film-like material.

  Hereinafter, the present invention will be described with reference to examples. In the following, “part” means “part by mass”, and “%” means “% by mass”. Further, the obtained cured film was evaluated by the following evaluation methods.

(1) Surface hardness In accordance with JIS K 5600, the surface of the cured film film is scratched at an angle of 45 degrees using a Mitsubishi Pencil Uni, and the maximum hardness without scratches is evaluated by pencil hardness. The surface hardness was determined.
○: F or more.
X: Less than F.

(2) Scratch resistance The state of the wound after placing the laminated film-like material on steel wool # 0000 so that the surface of the cured film of the film-like material faces and reciprocating 20 times with a load of 500 g / cm ² Was visually observed, and scratch resistance was evaluated according to the following criteria.
○: No scratch.
X: Scratch occurred.

(3) Stretchability The laminated film-like product was subjected to a tensile test using a Tensilon universal testing machine RTC-1250A manufactured by Orientec Co., Ltd. (sample dimensions: 80 mm × 15 mm, distance between chucks: 50 mm, pulling speed: 20 mm / min) ), And when the crack occurred in the cured film (visual judgment), the elongation at break was regarded as the elongation at break, and the extensibility was evaluated according to the following criteria.
○: Elongation at break 30% or more.
X: Elongation at break is less than 30%.

(4) Formability The mold following property at the time of molding when obtaining a laminated molded product was visually evaluated, and the moldability was judged according to the following criteria.
○: There are no cracks at the end of the truncated surface and the truncated surface.
Δ: Cracks occurred only at the edge of the truncated surface.
X: Cracks and whitening occurred on the truncated surface.

[Synthesis Example 1] (A) Synthesis of Component (UA-1) In a 2-liter four-necked flask, 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY) as a component (a1) CHDM, Mn: 144.2) 144 parts, (a2) 2,2,4-trimethylhexamethylene diisocyanate (manufactured by Evonik Degussa Japan Co., Ltd., trade name: VESTANATM TMDI, Mn: 210.1) 420 Then, 0.24 part of di-n-butyltin dilaurate (DBTDL) was added as a polyurethane-forming catalyst, and the temperature was raised to 80 ° C. with stirring. After confirming that the pellet-like 1,4-cyclohexanedimethanol was completely dissolved, 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: HEA, Mn: 116. 1) 232 parts were added and the reaction was continued for 10 hours while maintaining at 80 ° C. to obtain component (A) (UA-1). Table 1 shows the Mw and appearance of the obtained component (A) (UA-1).

The abbreviations in Table 1 indicate the following compounds.
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY CHDM, Mn: 144.2)
HB: hydrogenated bisphenol A (manufactured by Shin Nippon Rika Co., Ltd., trade name: rikabinol HB, Mn: 240)
TCDM: Tricyclodecane dimethanol (Oxea Japan Co., Ltd., trade name: TCD alcohol M, Mn: 196.3)
TPG: Tripropylene glycol (Asahi Glass Co., Ltd., trade name: TPG, Mn: 189)
PBA: Polypropylene oxide modified bisphenol A (Asahi Denka Kogyo Co., Ltd., trade name: Adeka Polyether BPX-1000, Mn: 1,000 (catalog value))
TMDI: 2,2,4-trimethylhexamethylene diisocyanate (Evonik Degussa Japan Co., Ltd., trade name: VESTANATM TMDI, Mn: 210.3)
IPDI: Isophorone diisocyanate (Evonik Degussa Japan Co., Ltd., trade name: VESTANAT IPDI, Mn: 222.2)
PETA: Pentaerythritol triacrylate (manufactured by Toa Gosei Co., Ltd., trade names: Aronix M-306, MN: 298)
DBTDL: di-n-butyltin dilaurate

[Synthesis Examples 2 to 6] Synthesis of (A) Component (UA-2) to (A) Component (UA-6) Synthesis Example 1 except that the type and blending amount of component (A) shown in Table 1 are used. The components (UA-2) to (A) (UA-6) were obtained in the same manner as above.

[Synthesis Example 7] (C) Synthesis of Component (CS-1) Isopropanol silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: IPA-) in a 3 liter four-necked flask equipped with a stirrer, thermometer and condenser. ST, dispersion medium: isopropanol, SiO ₂ concentration: 30%, average primary particle diameter: 12 nm (data disclosed by raw material manufacturer: equivalent surface area determined by BET method)) (hereinafter referred to as “IPA-ST”) 2,000 And 382 parts of 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) (hereinafter referred to as “KBM-503”) were added. Next, the temperature in the flask is raised while stirring, and 150 parts of ion-exchanged water are gradually added dropwise so as to maintain the reflux temperature at the same time as the reflux of the volatile components begins. KBM-503 was hydrolyzed with stirring for a period of time.

After completion of hydrolysis of KBM-503, volatile components such as alcohol and water are distilled off at normal pressure to obtain a solid content (917 parts in total of 600 parts of SiO _{2 of} IPA-ST and 317 parts of KBM-503). When about 60% was reached, 600 parts of toluene was added, and alcohol, water, and the like were azeotropically distilled together with toluene. Again, 1500 parts of toluene was added to the flask again, and the solvent was completely replaced to obtain a toluene dispersion. The solid concentration at this time was about 40%. Furthermore, while distilling off the toluene in the flask, the silanol group obtained by hydrolysis of the alkoxysilane of KBM-503 and the acidic hydroxyl group on the colloidal silica surface were reacted at 110 ° C. for 4 hours, and the solid content concentration was reduced to about The toluene solution of the polymerizable unsaturated double bond-containing inorganic fine particles (hereinafter referred to as “CS-1”) was obtained.

  The obtained CS-1 was a yellow, Newtonian fluid transparent and viscous liquid, and the viscosity at 25 ° C. was 30 mPa · s. Moreover, the solid content concentration of CS-1 was 60.0% in the heating residue. The solid content concentration was represented by (mass after heating (g) / mass before heating (g)) × 100 (%), and the heating condition was 105 ° C. for 3 hours.

[Synthesis Example 8] (D) Synthesis of Component (EP-1) 346 parts of bisphenol A diepoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YD8125) in a 5-liter 4-neck flask, acrylic acid (Mitsubishi 144 parts by Chemical Co., Ltd., trade name: 100% acrylic acid, 0.5 part hydroquinone monomethyl ether as a polymerization inhibitor, and dimethylaminoethyl methacrylate (Mitsubishi Rayon Co., Ltd., trade name: Acryester DM) as a polymerization inhibitor ) 2.5 parts was added, the temperature was raised to 95 ° C. with stirring, and the reaction was continued for 14 hours while maintaining the temperature at 95 ° C. When the acid value of the liquid in the flask became 1 mgKOH / g or less, the first-stage reaction was terminated to obtain an epoxy acrylate having two hydroxyl groups.

  Next, after the temperature inside the flask was lowered to 60 ° C., 705 parts of ethyl acetate (EA) was added as an organic solvent to the flask, and 0.11 part of di-n-butyltin dilaurate (DBTDL) was added as a polyurethane catalyst. While stirring, 212 parts of dicyclohexylmethane diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur W) was added dropwise over 2 hours. Reaction was continued for 5 hours after completion | finish of dripping of dicyclohexylmethane diisocyanate, and the urethane polyacrylate solution (EP-1) (solid content 50%) of Mw15,000 was obtained.

[Example 1]
80 parts of UA-1 as component (A), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl as component (B) -5 parts of propan-1-one (BASF Japan Co., Ltd., trade name: Irgacure 127), 33.3 parts of CS-1 as component (C), and 215 parts of ethyl acetate (EA) as an organic solvent are blended. An active energy ray-curable composition having a solid content concentration of 30% was obtained.

The obtained active energy ray-curable composition was placed on an easy-adhesion-treated surface of an easy-adhesion-treated polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4100, thickness 0.188 mm) as a film. Painted using coater # 10. After the easy-adhesion-treated polyethylene terephthalate film coated with the active energy ray-curable composition is dried by heating for 30 seconds in a hot air dryer at 100 ° C., an integrated light quantity of 300 mJ / cm ² (with a wavelength of 320 to 380 nm) is used. A laminated film-like material having a cured film of a smooth active energy ray-curable composition having a thickness of 3 μm (0.003 mm) by irradiating the active energy ray-curable composition by irradiating ultraviolet rays having an ultraviolet ray accumulated energy amount) (I) was obtained. Using the obtained laminated film-like material (A), the surface hardness, scratch resistance and stretchability were evaluated.

  Also, an acrylic film (trade name: acryloprene HBX-N47, thickness 0.125 mm, manufactured by Mitsubishi Rayon Co., Ltd.) was used as the film-like material, and the same as the laminated film-like material (A) except that the drying conditions were 80 ° C. Thus, a laminated film (b) having a cured film of a smooth active energy ray-curable composition having a thickness of 3 μm (0.003 mm) was obtained.

  The laminated film (b) is placed in the mold so that the surface of the cured film of the film (b) faces the inner wall of the mold, and then the film is formed by an infrared heater at a temperature of 120 ° C. for 20 seconds. The object (b) was preheated (the distance between the heater and the film was 30 mm). Then, it vacuum-sucked so that a film-form thing (2) might closely_contact | adhere to a metal mold | die surface, further heating, and made the film-form thing (2) follow a metal mold | die shape. The shape of the mold used was a truncated pyramid, the size of the truncated surface was 100 mm × 100 mm, the size of the bottom surface was 108 mm × 117 mm, the depth was 10 mm, and the curvature radius of the edge of the truncated surface Was 3 mm.

  Acrylic resin (Mitsubishi Rayon Co., Ltd., trade name: Acrypet VH) is injected into a mold with a film-like material (b) in close contact with the surface under conditions of a molding temperature of 220 to 240 ° C. and a mold temperature of 70 ° C. Then, molding was performed to obtain a laminated molded article having a cured film of the active energy ray curable composition. The moldability evaluation results are shown in Table 2.

[Examples 2 to 12 and Comparative Example 1]
An active energy ray-curable composition was prepared in the same manner as in Example 1 except that the composition and composition of each component of the active energy ray-curable composition shown in Table 2 were used, and a laminated film having a cured film having a thickness of 3 μm. Articles and laminated molded products were obtained. The evaluation results are shown in Table 2.

The numerical values in parentheses for the component (C) and the component (D) in Table 2 indicate the solid content (parts).
The abbreviations in Table 2 indicate the following compounds.
UA-1: polyurethane compound of Synthesis Example 1 UA-2: polyurethane compound of Synthesis Example 2 UA-3: polyurethane compound of Synthesis Example 3 UA-4: polyurethane compound of Synthesis Example 4 UA-5: polyurethane compound of Synthesis Example 5 UA-6: Polyurethane compound of Synthesis Example 6 IT-1: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane- 1-on (trade name: Irgacure 127, manufactured by BASF Japan Ltd.)
CS-1: Toluene solution of polymerizable unsaturated double bond-containing inorganic fine particles of Synthesis Example 7 CS-2: Organic compound-modified colloidal silica (manufactured by Big Chemie Japan Co., Ltd., trade name: NANOBYK-3650, effective Ingredient 32%)
TMPTA: Trimethylolpropane triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 295)
EP-1: Polyurethane compound DPHA of Synthesis Example 8: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad DPHA)
EA: ethyl acetate

As is apparent from the results of Examples 1 to 12, the cured film of the active energy ray-curable composition obtained in the present invention is excellent in surface hardness, scratch resistance and stretchability, and formability when obtaining a laminated molded product. It turns out that it is also excellent. In contrast, Comparative Example 1
Then, the cured film of the active energy ray-curable composition obtained under the conditions not satisfying the requirements of the components (A) and (C) in the present invention was inferior to those of the examples in terms of stretchability and moldability.

Claims (4)

An active energy ray-curable composition containing a polyurethane compound (A) obtained by reacting the following components (a1), (a2) and (a3), a photopolymerization initiator (B) and inorganic particles (C).
(A1) component: diol having a ring structure in the molecule and a number average molecular weight of 50 to 500 (a2) component: diisocyanate (a3) component: having one hydroxyl group and one or more photopolymerizable groups in the molecule Compound   A laminated film-like product obtained by laminating a cured film of the active energy ray-curable composition according to claim 1 on one surface of the film-like product.   A laminated molded product in which the laminated film-like product according to claim 2 is laminated on at least one surface of the molded product so that the surface of the film-like product and the surface of the molded product are in contact with each other.   A laminated molded article in which the cured film of the active energy ray-curable composition according to claim 1 is laminated on the surface of the molded article.