CN107406690B - Resin composition for forming hard coat layer and cured product thereof - Google Patents
Resin composition for forming hard coat layer and cured product thereof Download PDFInfo
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- CN107406690B CN107406690B CN201680011522.9A CN201680011522A CN107406690B CN 107406690 B CN107406690 B CN 107406690B CN 201680011522 A CN201680011522 A CN 201680011522A CN 107406690 B CN107406690 B CN 107406690B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention provides a resin composition for forming a hard coat layer, which can obtain a cured product with suppressed occurrence of curling and higher surface hardness and scratch resistance. The resin composition for forming a hard coat layer of the present invention contains: a polyfunctional alicyclic epoxy compound (A), a polyfunctional (meth) acrylic compound (B), surface-modified inorganic particles (C), a photo cation polymerization initiator (D), and a photo radical polymerization initiator (E), wherein the content of the (A) is 3 to 35 wt% of the sum (100 wt%) of the contents of the (A) and the (B).
Description
Technical Field
The present invention relates to a resin composition for forming a hard coat layer and a cured product thereof. The present invention also relates to a coated article obtained using the resin composition for forming a hard coat layer. This application claims priority to Japanese application laid-open application No. 2015-086412 at 21/4/2015, the contents of which are incorporated herein by reference.
Background
By attaching a protective film to a liquid crystal display such as a liquid crystal display, an organic EL display, or a plasma display, the effects of preventing damage to a screen, preventing fingerprints from adhering to the screen, and easily wiping off dirt adhering to the screen can be obtained. A hard coat layer for imparting scratch resistance is formed on the surface of the protective film. Accordingly, in recent years, as the demand for increasing the surface hardness of the liquid crystal protective film has increased, the performance of the hard coat layer has been required to be improved.
As a method for improving the surface hardness of the hard coat layer, multifunctionalization of the curable group of the curable compound forming the hard coat layer has been widely employed. However, it is known that a polyfunctional curable compound causes an increase in resin density, i.e., shrinkage during curing, before and after curing. Therefore, there is a problem that curing shrinkage becomes more remarkable as multifunctionalization occurs, and the protective film exhibits curling properties.
As a method for improving the scratch resistance of a hard coat layer, a method of blending inorganic particles such as alumina, silica, and titanium oxide in a curable compound, a so-called organic-inorganic hybrid method, is known (patent document 1).
However, when a coating film is prepared by dispersing inorganic particles in a resin, there is a possibility that phenomena such as the loss of the inorganic particles, the increase in haze, and the occurrence of brittleness are observed in the coating film after curing (cured coating film). This is considered to be caused by poor compatibility between organic and inorganic substances. As a method for improving the compatibility between an organic material and an inorganic material, a method using a nanofiller in which the particle size of inorganic particles is reduced to a nanometer size is known (patent document 2). However, when inorganic particles having a nano-size are used, dispersion stability is lowered, inorganic particles are likely to aggregate with each other, and it is difficult to maintain transparency of the cured coating film. Further, a method of using a surface-modified inorganic filler in which a shell of an inorganic particle is surface-modified with an organic material is also known (patent document 3). However, when inorganic particles having surfaces modified with organic substances are used, it is difficult to increase the surface hardness of the cured coating film, and the surface hardness may be decreased.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (Kokoku) No. 2-60696
Patent document 2: japanese laid-open patent publication No. 2005-76005
Patent document 3: japanese patent laid-open publication No. 2003-34761
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a resin composition for forming a hard coat layer, which can obtain a cured product having higher surface hardness and scratch resistance while suppressing the occurrence of curling properties.
The term "crimpability" refers to a property of causing a curl to the substrate when a film of a cured product (cured coating film) is formed on the substrate, and the term "low crimpability" refers to a property of not easily causing a curl to the substrate.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, they have found that a cured product having a suppressed occurrence of curling properties, that is, low curling properties (or low curing shrinkage properties), and higher surface hardness and scratch resistance can be obtained when a resin composition containing a polyfunctional alicyclic epoxy compound, a polyfunctional (meth) acrylic compound, and inorganic particles having a functional group reactive with an epoxy group of the polyfunctional alicyclic epoxy compound and/or a (meth) acryloyl group of the polyfunctional (meth) acrylic compound at a specific ratio is irradiated with an active energy ray. The present invention has been completed based on these findings.
That is, the present invention provides a resin composition for forming a hard coat layer, comprising: the surface-modified inorganic particles (C) are characterized in that the surface-modified inorganic particles (C) have an average particle diameter (based on a dynamic light scattering method) of 0.1 to 100nm and have a functional group reactive with an epoxy group and/or a (meth) acryloyl group on the surface thereof, a photo cation polymerization initiator (D), and a photo radical polymerization initiator (E), and the content of (A) is 3 to 35 wt% of the sum (100 wt%) of the contents of (A) and (B).
The present invention also provides the resin composition for forming a hard coat layer, wherein the content of (C) is 5 to 40 parts by weight based on 100 parts by weight of the total content of (A) and (B).
The present invention also provides the resin composition for forming a hard coat layer, wherein the concentration of (meth) acryloyl groups in the total amount of (a), (B), and (C) contained in the resin composition for forming a hard coat layer is greater than 5.0 mmol/g.
The present invention also provides the resin composition for forming a hard coat layer, wherein the inorganic particles in the surface-modified inorganic particles (C) are silica.
The present invention also provides the resin composition for forming a hard coat layer, further comprising at least one compound selected from the group consisting of: silicon compounds, perfluoroalkyl group-containing (meth) acrylic compounds, silyl group-containing (meth) acrylic compounds, polyether-modified (meth) acrylic compounds, silicon-modified poly (meth) acrylates, polyether-modified poly (meth) acrylates, perfluoroalkyl group-containing polyether-modified (meth) acrylates, acrylic-modified polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, perfluoroalkyl group-containing polydimethylsiloxanes, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxanes.
The present invention also provides a cured product of the resin composition for forming a hard coat layer.
The present invention also provides a coated article having a hard coat layer formed from a cured product of the resin composition for forming a hard coat layer on a surface of an article.
That is, the present invention relates to the following.
[1] A resin composition for forming a hard coat layer, comprising: the surface-modified inorganic particles (C) are characterized in that the surface-modified inorganic particles (C) have an average particle diameter (based on a dynamic light scattering method) of 0.1 to 100nm and have a functional group reactive with an epoxy group and/or a (meth) acryloyl group on the surface thereof, a photo cation polymerization initiator (D), and a photo radical polymerization initiator (E), and the content of (A) is 3 to 35 wt% of the sum (100 wt%) of the contents of (A) and (B).
[2] The resin composition for forming a hard coat layer according to [1], wherein (A) is a compound represented by formula (I) (alicyclic epoxy compound).
[3] The resin composition for forming a hard coat layer according to [1], wherein (A) is at least one compound selected from the group consisting of: (3,4,3',4' -diepoxy) bicyclohexane, bis (3, 4-epoxycyclohexylmethyl) ether, 1, 2-epoxy-1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, 2-bis (3, 4-epoxycyclohexan-1-yl) propane, 1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, and compounds represented by formulae (I-1) to (I-10).
[4] The resin composition for forming a hard coat layer according to [1], wherein (A) is 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate and/or (3,4,3',4' -diepoxy) bicyclohexane.
[5] The resin composition for forming a hard coat layer according to any one of the above [1] to [4], wherein (B) is a compound having 3 or more (e.g., 3 to 12, preferably 5 or more, and particularly preferably 5 to 10) (meth) acryloyl groups.
[6] The resin composition for forming a hard coat layer according to any one of the above [1] to [5], wherein the molecular weight of (B) is 300 to 13000.
[7] The resin composition for forming a hard coat layer according to any one of the above [1] to [6], wherein the weight average molecular weight (in terms of standard polystyrene based on GPC) of (B) is 400 to 13000.
[8] The resin composition for forming a hard coat layer according to any one of the above [1] to [7], wherein (B) is dipentaerythritol poly (meth) acrylate or a derivative thereof.
[9] The resin composition for forming a hard coat layer according to any one of the above [1] to [8], wherein the inorganic particles in (C) are silica, titania, alumina, or zirconia.
[10] The resin composition for forming a hard coat layer according to any one of the above [1] to [8], wherein the inorganic particles in (C) are silica.
[11] The resin composition for forming a hard coat layer according to any one of the above [1] to [10], wherein the inorganic particles in (C) have an average particle diameter (by a dynamic light scattering method) of 1 to 10 nm.
[12] The resin composition for forming a hard coat layer according to any one of the above [1] to [11], wherein the functional group reactive with an epoxy group and/or a (meth) acryloyl group in (C) is a group selected from a hydroxyl group, a glycidyl ether group and an alicyclic epoxy group (preferably a cyclohexenyl oxide group).
[13] The resin composition for forming a hard coat layer according to any one of [1] to [12], further comprising a functional group reactive with an epoxy group and/or a (meth) acryloyl group selected from the group consisting of: at least one compound selected from the group consisting of a silicon compound, a perfluoroalkyl group-containing (meth) acrylic compound, a silyl group-containing (meth) acrylic compound, a polyether-modified (meth) acrylic compound, a silicon-modified poly (meth) acrylate, a polyether-modified poly (meth) acrylate, a perfluoroalkyl group-containing polyether-modified (meth) acrylate, an acrylic-modified polydimethylsiloxane, a polyether-modified polydimethylsiloxane, a perfluoroalkyl group-containing polydimethylsiloxane, and a polyether-modified perfluoroalkyl group-containing polydimethylsiloxane.
[14] The resin composition for forming a hard coat layer according to any one of the above [1] to [12], further comprising a hydroxyl group-containing silicon-modified poly (meth) acrylate.
[15] The resin composition for forming a hard coat layer according to any one of the above [1] to [14], wherein the content of (A) is 3 to 50% by weight of the total nonvolatile content in the resin composition.
[16] The resin composition for forming a hard coat layer according to any one of the above [1] to [15], wherein the content of (B) is 40 to 95% by weight of the total nonvolatile components contained in the resin composition.
[17] The resin composition for forming a hard coat layer according to any one of [1] to [16], wherein the concentration of the (meth) acryloyl group in the total amount of (A), (B), and (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol/g.
[18] The resin composition for forming a hard coat layer according to any one of the above [1] to [17], wherein the content of (C) is 1 to 30% by weight based on the total amount of nonvolatile components contained in the resin composition.
[19] The resin composition for forming a hard coat layer according to any one of [1] to [18], wherein the content of (C) is 5 to 40 parts by weight based on 100 parts by weight of the total content of (A) and (B).
[20] The resin composition for forming a hard coat layer according to any one of [1] to [19], wherein the sum of the contents of (A) and (C) is 5 to 60% by weight of the total (100% by weight) of (A), (B) and (C).
[21] The resin composition for forming a hard coat layer according to any one of the above [1] to [20], wherein the content of (D) is 1 to 10 parts by weight based on 100 parts by weight of the cationically curable compound (particularly the polyfunctional alicyclic epoxy compound (A)) contained in the resin composition.
[22] The resin composition for forming a hard coat layer according to any one of [1] to [21], wherein the content of (E) is 1 to 10 parts by weight based on 100 parts by weight of a radically curable compound (particularly, a polyfunctional (meth) acrylic compound (B)) contained in the resin composition.
[23] The resin composition for forming a hard coat layer according to any one of [1] to [22], wherein the resin composition for forming a hard coat layer comprises at least one compound [ particularly a hydroxyl group-containing silicon-modified poly (meth) acrylate, a polyether-modified polydimethylsiloxane, a perfluoroalkyl group-containing polydimethylsiloxane, and a polyether-modified perfluoroalkyl group-containing polydimethylsiloxane [ at least one compound selected from the group consisting of silicon compounds, perfluoroalkyl group-containing (meth) acrylic compounds, silyl group-containing (meth) acrylic compounds, polyether-modified (meth) acrylic compounds, silicon-modified poly (meth) acrylates, polyether-modified poly (meth) acrylates, perfluoroalkyl group-containing poly (meth) acrylates, and polyether-modified perfluoroalkyl group-containing polydimethylsiloxanes ] with respect to the total amount (100 parts by weight) of (A), (B), and (C) 0.01 to 10 parts by weight.
[24] A cured product of the resin composition for forming a hard coat layer according to any one of [1] to [23 ].
[25] A coated article having a hard coat layer formed from a cured product of the resin composition for forming a hard coat layer according to any one of [1] to [23] on a surface of an article.
[26] A coated article obtained by applying the resin composition for forming a hard coat layer according to any one of [1] to [23] to a surface of an article and curing the applied resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The resin composition for forming a hard coat layer of the present invention, having the above-described configuration, can form a cured product having high surface hardness, excellent abrasion resistance, and low curling properties (or low curing shrinkage properties) by irradiation with active energy rays, and can be suitably used as a resin composition for forming a hard coat layer on the surface of a plastic film such as TAC (cellulose triacetate) or PET (polyethylene terephthalate). The resin composition for forming a hard coat layer of the present invention can be preferably used as a resin composition for forming a hard coat layer of a glass substrate, and when used for this purpose, the resin composition can exert an effect of imparting high surface hardness and excellent scratch resistance and also exert an effect of preventing breakage of a glass substrate.
Drawings
FIG. 1 is a schematic diagram for explaining a method of evaluating curling properties in examples.
Detailed Description
The resin composition for forming a hard coat layer (hereinafter also referred to as "resin composition") of the present invention contains a polyfunctional alicyclic epoxy compound (a) and a polyfunctional (meth) acrylic compound (B). In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid (either or both of acrylic acid and methacrylic acid), and the same applies to (meth) acrylic acid esters and the like.
[ polyfunctional alicyclic epoxy Compound (A) ]
The polyfunctional alicyclic epoxy compound (a) is a cationically curable compound having an alicyclic structure and 2 or more epoxy groups in 1 molecule. In the resin composition of the present invention, the polyfunctional alicyclic epoxy compound (a) may be used singly or in combination of two or more.
Specific examples of the polyfunctional alicyclic epoxy compound (a) include:
(i) a compound having an epoxy group (alicyclic epoxy group) formed by adjacent 2 carbon atoms constituting an alicyclic ring and an oxygen atom;
(ii) a compound having an epoxy group directly singly bonded to an alicyclic ring;
(iii) a compound having an alicyclic ring and a glycidyl group; and so on.
Examples of the (i) compound having an alicyclic epoxy group include: a compound represented by the following formula (I) (alicyclic epoxy compound).
[ chemical formula 1]
In the formula (I), X represents a single bond or a linking group (a divalent group having 1 or more atoms). Examples of the linking group include: a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bonds have been epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a group in which a plurality of these groups are linked, and the like. In the formula (I), 1 or more of the carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) may be bonded to a substituent such as an alkyl group.
Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include: methylene, methyl methylene, dimethyl methylene, ethylene, propylene, trimethylene and the like. Examples of the divalent alicyclic hydrocarbon group include: cycloalkylene (including cycloalkylene) such as 1, 2-cyclopentylene, 1, 3-cyclopentylene, cyclopentylidene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, cyclohexylidene and the like.
Examples of the alkenylene group in the above-mentioned alkenylene group in which a part or all of the carbon-carbon double bonds have been epoxidized (also referred to as "epoxidized alkenylene group") include: and linear or branched alkenylene groups having 2 to 8 carbon atoms such as vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, octenylene, and the like. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds have been epoxidized.
The linking group in X is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include: -CO-, -O-CO-O-, -COO-, -O-, -CONH-, epoxyalkenylene; a group formed by connecting a plurality of these groups; and groups in which 1 or 2 or more of these groups are linked to 1 or 2 or more of the divalent hydrocarbon groups.
As representative examples of the compounds represented by the above formula (I), there can be mentioned: (3,4,3',4' -diepoxy) bicyclohexane, bis (3, 4-epoxycyclohexylmethyl) ether, 1, 2-epoxy-1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, 2-bis (3, 4-epoxycyclohexan-1-yl) propane, 1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, or compounds represented by the following formulae (I-1) to (I-10). L in the formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable. N in the following formulae (I-5), (I-7), (I-9) and (I-10)1～n8Each represents an integer of 1 to 30.
[ chemical formula 2]
[ chemical formula 3]
As (i) the compound having an alicyclic epoxy group, for example: commercially available products such as "CELLOXIDE 2021P" and "CELLOXIDE 2081" (manufactured by Daicel, Inc., supra).
Examples of the compound (ii) having an epoxy group directly singly bonded to an alicyclic ring include: and a compound represented by the following formula (II).
[ chemical formula 4]
In the formula (II), R' is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of p-polyol, and p and n respectively represent natural numbers. As p-polyol [ R' - (OH)p]Examples thereof include polyhydric alcohols (e.g., alcohols having 1 to 15 carbon atoms) such as 2, 2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each square bracket (outer bracket) may be the same or different. Specific examples of the compound represented by the formula (II) include 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol [ for example, the trade name "EHPE 3150" ((manufactured by Daicel Co., Ltd.) ]]And the like.
Examples of the compound (iii) having an alicyclic group and a glycidyl group include: hydrogenated aromatic glycidyl ether-based epoxy compounds such as a compound obtained by hydrogenating a bisphenol a-based epoxy compound (hydrogenated bisphenol a-based epoxy compound), a compound obtained by hydrogenating a bisphenol F-based epoxy compound (hydrogenated bisphenol F-based epoxy compound), a hydrogenated bisphenol-based epoxy compound, a hydrogenated phenol novolac-based epoxy compound, a hydrogenated cresol novolac-based epoxy compound of bisphenol a, a hydrogenated naphthalene-based epoxy compound, and a hydrogenated epoxy compound of an epoxy compound obtained from triphenol methane.
The polyfunctional alicyclic epoxy compound (a) is preferably (I) a compound having an alicyclic epoxy group, particularly preferably 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate [ the compound represented by the above formula (I-1), trade name "CELLOXIDE 2021P" ((manufactured by Daicel corporation) ], etc. ], and (3,4,3',4' -diepoxy) bicyclohexane, in view of obtaining a cured product having low curling properties, high surface hardness, and excellent transparency.
(A) The content (blending amount) of (b) is, for example, 3 to 50% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention, and the upper limit is preferably 38% by weight, particularly preferably 33% by weight, most preferably 29% by weight, and particularly preferably 25% by weight. The lower limit is preferably 6% by weight, particularly preferably 10% by weight, most preferably 13% by weight, and particularly preferably 17% by weight.
The content (amount of the component (A) is 3 to 35 wt%, preferably 10 to 33 wt%, particularly preferably 13 to 29 wt%, most preferably 17 to 25 wt% of the sum (100 wt%) of the contents (A) and (B).
By controlling the content of (a) in the above range, the effect of reducing curling properties while maintaining scratch resistance can be obtained. (A) When the content of (B) exceeds the above range, the content of the polyfunctional (meth) acrylic compound (B) described later becomes small, so that the anti-curling property is exhibited and it is difficult to obtain a cured product having low curling property. In addition, the scratch resistance tends to decrease. On the other hand, when the content of (a) is less than the above range, the content of the polyfunctional (meth) acrylic compound (B) described later becomes excessive, and thus positive curling properties occur, and it is difficult to obtain a cured product having low curling properties.
[ polyfunctional (meth) acrylic compound (B) ]
The polyfunctional (meth) acrylic compound (B) in the present invention is a radically curable compound having 2 or more (meth) acryloyl groups in 1 molecule. In the resin composition of the present invention, the polyfunctional (meth) acrylic compound (B) may be used singly or in combination of two or more.
The number (total number) of acryloyl groups and/or methacryloyl groups in the molecule of the polyfunctional (meth) acrylic compound (B) is 2 or more, for example, 2 to 15, more preferably 3 or more (for example, 3 to 12), and still more preferably 5 or more (for example, 5 to 10).
The molecular weight of the polyfunctional (meth) acrylic compound (B) is, for example, 300 to 13000, preferably 400 to 13000, particularly preferably 500 to 10000, most preferably 500 to 3000. The weight average molecular weight (Mw) of the polyfunctional (meth) acrylic compound (B) is, for example, 400 to 13000, preferably 500 to 10000, and particularly preferably 500 to 3000. When the molecular weight is less than 300 and/or the weight average molecular weight is less than 400, the curling property of the cured product may be increased. On the other hand, when the molecular weight and/or the weight average molecular weight exceeds 13000, the surface hardness of the cured product may be lowered, and the function as a surface coating (particularly, a hard coat) of a protective film may not be exerted. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by GPC.
Examples of the polyfunctional (meth) acrylic compound (B) include: non-aromatic (meth) acrylates such as aliphatic (meth) acrylates (linear or branched aliphatic (meth) acrylates) and alicyclic (meth) acrylates); aromatic (meth) acrylates, and the like. Among them, in the present invention, from the viewpoint of non-coloring property of the cured product, a non-aromatic (meth) acrylate is preferable, and an aliphatic (meth) acrylate is particularly preferable.
Specifically, examples of the polyfunctional (meth) acrylic compound (B) include: 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, and mixtures thereof, Difunctional (meth) acrylates such as 2, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane and derivatives thereof; ethoxylated isocyanurate tri (meth) acrylate,. epsilon. -caprolactone-modified tris (2- (meth) acryloyloxyethyl) isocyanurate, glycerin tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, propoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acrylate of a 3-mole ethylene oxide adduct of trimethylolpropane, tri (meth) acrylate of a 3-mole propylene oxide adduct of trimethylolpropane, tri (meth) acrylate of a 6-mole ethylene oxide adduct of trimethylolpropane, tri (meth) acrylate of a 6-mole propylene oxide adduct of trimethylolpropane, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethylene oxide, Pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate (e.g., dipentaerythritol hexa (meth) acrylate, dipentaerythritol caprolactone adduct hexa (meth) acrylate, and the like), and derivatives thereof, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polydiene (meth) acrylate (e.g., polybutadiene (meth) acrylate, and the like), melamine (meth) acrylate, polyacetal (meth) acrylate, and the like.
As the polyfunctional (meth) acrylic compound (B), for example: commercially available products such as "DPHA" (manufactured by Daicel-Allnex, Inc.).
The concentration of the (meth) acryloyl group (for example, the (meth) acryloyl group contained in the polyfunctional (meth) acrylic compound (B)) in the total amount of (a), (B), and (C) contained in the resin composition of the present invention is, for example, greater than 5.0 mmol/g (for example, greater than 5.0 mmol/g and 10.0 mmol/g or less), preferably 5.5 mmol/g or more, more preferably 6.0 mmol/g or more, particularly preferably 6.5 mmol/g or more, and most preferably 7.0 mmol/g or more. The upper limit of the concentration of the (meth) acryloyl group is preferably 9.5 mmol/g, more preferably 9.0 mmol/g, still more preferably 8.5 mmol/g, particularly preferably 8.0 mmol/g, and most preferably 7.5 mmol/g.
(B) The content of (b) is, for example, 40 to 95% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention, and the upper limit is preferably 90% by weight, more preferably 85% by weight, particularly preferably 80% by weight, and most preferably 75% by weight. The lower limit is preferably 45% by weight, more preferably 50% by weight, and particularly preferably 55% by weight.
The content (amount of the component (B) is 65 to 97 wt%, preferably 65 to 94 wt%, more preferably 65 to 90 wt%, particularly preferably 65 to 87 wt%, most preferably 68 to 83 wt%, and particularly preferably 73 to 83 wt% of the sum (100 wt%) of the contents (A) and (B).
By controlling the content of (B) in the above range, the effect of reducing curling properties while maintaining scratch resistance can be obtained. (B) When the content of (b) exceeds the above range, the content of the polyfunctional alicyclic epoxy compound (a) becomes small, and thus positive curling properties appear, and it is difficult to obtain a cured product with low curling properties. On the other hand, when the content of (B) is less than the above range, the content of the polyfunctional alicyclic epoxy compound (a) becomes excessive, so that the anti-curling property is developed, and it is difficult to obtain a cured product having a low curling property. In addition, the scratch resistance tends to be lowered.
[ surface-modified inorganic particles (C) ]
The surface-modified inorganic particles (C) in the present invention are inorganic particles having a reactive functional group (i.e., a functional group reactive with an epoxy group, a functional group reactive with a (meth) acryloyl group, or a functional group reactive with an epoxy group and a (meth) acryloyl group) on the surface thereof, with respect to the epoxy group and/or the (meth) acryloyl group of the polyfunctional alicyclic epoxy compound (a). The surface-modified inorganic particles (C) of the present invention have the reactive functional group described above, and therefore have excellent compatibility with organic substances. In addition, the dispersion is excellent, and the aggregation of inorganic particles can be prevented. Among them, in the case where the surface-modified inorganic particles (C) of the present invention have a reactive functional group with an epoxy group, they are bonded to the polyfunctional alicyclic epoxy compound (a), in the case where the surface-modified inorganic particles (C) of the present invention have a reactive functional group with a (meth) acryloyl group, they are bonded to the polyfunctional (meth) acrylic compound (B), and in the case where the surface-modified inorganic particles (C) of the present invention have a reactive functional group with an epoxy group and a (meth) acryloyl group, they are bonded to the polyfunctional alicyclic epoxy compound (a) and the polyfunctional (meth) acrylic compound (B), so that no inorganic particle is broken from the cured product, and excellent scratch resistance can be imparted to the cured product. Further, the cured product can be prevented from increasing in haze or from becoming brittle. The surface-modified inorganic particles (C) may be used singly or in combination of two or more.
The inorganic particles include transparent inorganic particles such as silica, titania, alumina, and zirconia. In the present invention, among these, silica is preferable because it can suppress coloring of a cured product, and does not inhibit curing of the curable compound (i.e., the polyfunctional alicyclic epoxy compound (a) and the polyfunctional (meth) acrylic compound (B)) and also does not cause decomposition of the curable compound and a polymer thereof.
The inorganic particles have an average particle diameter (based on a dynamic light scattering method) of 0.1 to 100nm, preferably 1 to 50nm, and particularly preferably 3 to 20 nm. When the average particle diameter exceeds the above range, transparency tends to be lowered. On the other hand, when the average particle diameter is less than the above range, scratch resistance tends to be difficult to obtain.
Examples of the reactive functional group with an epoxy group and/or a (meth) acryloyl group include: (meth) acryloyl groups, glycidyl ether groups, alicyclic epoxy groups, oxetane groups, vinyl ether groups, thienylpropyl groups, vinyl groups, hydroxyl groups, and the like. In the present invention, among them, from the viewpoint of improving scratch resistance of the polyfunctional alicyclic epoxy compound (a), a group having excellent reactivity with an epoxy group is preferable, and a hydroxyl group, a glycidyl ether group, and an alicyclic epoxy group (for example, an oxicyclohexenyl group) are particularly preferable.
In the present invention, commercially available products such as the trade name "Y10C-MFK" ((manufactured by Admatechs, Ltd.) can be suitably used.
(C) The content (blending amount) of (b) is, for example, 1 to 30% by weight, preferably 3 to 25% by weight, particularly preferably 4 to 20% by weight, and most preferably 5 to 15% by weight of the total amount of nonvolatile components (components other than the solvent) contained in the resin composition of the present invention.
The content (blending amount) of (C) is, for example, 5 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 7 to 25 parts by weight, particularly preferably 10 to 20 parts by weight, and most preferably 10 to 15 parts by weight, based on 100 parts by weight of the total content of (A) and (B).
The sum of the contents of (A) and (C) is, for example, 5 to 60% by weight of the sum (100% by weight) of (A), (B) and (C), and the upper limit is preferably 55% by weight, particularly preferably 50% by weight, and most preferably 40% by weight. The lower limit is preferably 10% by weight, particularly preferably 15% by weight, most preferably 20% by weight, and particularly preferably 25% by weight.
When (C) is contained in the above range, a cured product having abrasion resistance, high hardness and low curling properties can be obtained, which is preferable from the viewpoint of the compatibility. (C) When the content of (b) is less than the above range, the scratch resistance tends to be lowered. On the other hand, when the content of (C) exceeds the above range, transparency tends to be impaired.
When the resin composition of the present invention contains, as the surface-modified inorganic particles (C), inorganic particles having a reactive functional group with an epoxy group of the polyfunctional alicyclic epoxy compound (a) on the surface, the resin composition can be prepared by adding and mixing the polyfunctional alicyclic epoxy compound (a) and the surface-modified inorganic particles (C) separately, but when the content of the surface-modified inorganic particles (C) is large, the composition obtained in this way tends to easily generate haze. In addition, in general, when the surface-modified inorganic particles (C) are added to the resin composition, they are added in a state of being dispersed in a solvent, but if the surface-modified inorganic particles (C) are added in a large amount, a large amount of solvent needs to be added along with it, and therefore, when the amount of solvent added is set to a low value, the amount of surface-modified inorganic particles (C) that can be added is considerably limited. Therefore, it is preferable to use a material obtained by reacting a reactive functional group (for example, a hydroxyl group) with an epoxy group of the surface-modified inorganic particles (C) with an epoxy group of the polyfunctional alicyclic epoxy compound (a), a material obtained by dispersing the surface-modified inorganic particles (C) in the polyfunctional alicyclic epoxy compound (a) without a solvent, or a material obtained by mixing the surface-modified inorganic particles (C) dispersed in a solvent with the polyfunctional alicyclic epoxy compound (a) and then removing the solvent. As a material obtained by reacting the polyfunctional alicyclic epoxy compound (a) with the surface-modified inorganic particles (C), for example, a product name "NANOPOXC 620" (manufactured by EVONIC corporation) or the like can be suitably used. As a material in which the surface-modified inorganic particles (C) having a functional group reactive with an epoxy group are dispersed in the polyfunctional alicyclic epoxy compound (a) without a solvent, for example, "Y10C-JFS" ((manufactured by adatech corporation)) or the like can be suitably used.
[ photo cation polymerization initiator (D) ]
The photo cation polymerization initiator is a compound that generates an acid by irradiation with light to initiate a curing reaction of a cation curable compound contained in a resin composition, and includes a cation portion that absorbs light and an anion portion that is a generation source of the acid.
Examples of the photo cation polymerization initiator include: diazo
Salt compound and iodine
Salt compounds, sulfonium salt compounds,
Salt compound, selenium salt compound, oxygen
Salt compounds, ammonium salt compounds, bromine salt compounds, and the like.
Among them, in the present invention, a sulfonium salt compound is preferably used because it can form a cured product having excellent curability. Examples of the cation portion of the sulfonium salt compound include: aryl sulfonium ions (particularly triarylsulfonium ions) such as (4-hydroxyphenyl) methylbenzyl sulfonium ion, triphenyl sulfonium ion, diphenyl [4- (phenylthio) phenyl ] sulfonium ion, 4- (4-biphenylthio) phenyl-4-biphenylphenyl sulfonium ion, and tri-p-tolylsulfonium ion.
Examples of the anion portion of the photo cation polymerization initiator include: [ (Y)sB(Phf)4-s]-(wherein Y represents a phenyl group or a biphenyl group; Phf represents a phenyl group in which at least 1 of hydrogen atoms is substituted by at least 1 member selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group and a halogen atom; s is an integer of 0 to 3), BF4 -、[(Rf)tPF6-t]-(wherein Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and t represents an integer of 0 to 5), and AsF6 -、SbF6 -、SbF5OH-And the like.
Examples of the photo-cationic polymerization initiator in the present invention include: (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfinatotetrakis (pentafluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylthio) phenylthion]-4-biphenylphenylsulfonium phenyltris (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl]Sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl]Sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl]Sulfonium hexafluorophosphate, 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonium) phenyl]Thioether phenyl tris (pentafluorophenyl) borate, [4- (2-thioxanthylthio) phenyl]Phenyl-2-thioxanthene ketosulfonium phenyl tris (pentafluorophenyl) borate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, the trade names "CYRACURE UVI-6970", "CYRACURE UVI-6974", "CYRACURE UVI-6990", "CYRACURE UVI-950" (manufactured by Union carbide, Inc., USA), "Irgacure 250", "Irgacure 261", "Irgacure 264" (manufactured by BASF, Inc., CG-24-61 "(manufactured by Ciba-Geigy, Inc.)," Optomer SP-150 "," Optomer SP-151 "," Optomer SP-170 "," Optomer SP-171 "(manufactured by ADEKA, Inc.)," DAICAT II "((manufactured by DAICAL, Inc.)," UVAC1590 "," UVAC1591 "(manufactured by Daicel-Cytec, Inc. (manufactured by CI-2064)," C-2639 ", and" C15939 "(manufactured by DAICA, IncI-2624 "," CI-2481 "," CI-2734 "," CI-2855 "," CI-2823 "," CI-2758 "," CIT-1682 "(manufactured by Nippon Caoda Co., Ltd.) and" PI-2074 "(manufactured by Rhodia, tetrakis (pentafluorophenyl) borate toluoylcumyl iodide
Salt), "FFC 509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (manufactured by Midori Kagaku Co., Ltd. (supra), "CD-1010", "CD-1011", "CD-1012" (manufactured by Sartomer America Co., Ltd. (supra), "CPI-100P" and "CPI-101A" (manufactured by SAN-APRO Co., Ltd.) (supra). These may be used alone in 1 kind, or more than 2 kinds may be used in combination.
The content of the photo-cationic polymerization initiator (D) in the resin composition of the present invention is, for example, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, and particularly preferably 2 to 4 parts by weight, based on 100 parts by weight of the cationically curable compound (particularly the polyfunctional alicyclic epoxy compound (a)) contained in the resin composition. When the content of the photo cation polymerization initiator (D) is less than the above range, there is a possibility that curing failure is caused. On the other hand, when the content of the photo cation polymerization initiator (D) exceeds the above range, the cured product tends to be colored easily.
[ photo radical polymerization initiator (E) ]
The photo radical polymerization initiator is a compound that generates radicals by irradiation with light to initiate a curing reaction of a radical curable compound contained in the resin composition, and examples thereof include: benzophenone, benzyl acetophenone (acetophenone benzyl), benzyl dimethyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfide, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kagaku K.K.; trade name "KAYACURE EPA", etc.), 2, 4-diethylthioxanthone (manufactured by Nippon Kagaku K.K.; trade name "KAYACURE;)DETX ″), 2-methyl-1- [4- (methyl) phenyl]2-morpholino-acetone-1 (product name "Irgacure 907" manufactured by Ciba-Geigy Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (product name "Irgacure 184" manufactured by Ciba-Geigy Co., Ltd.), 2-amino-2-benzoyl-1-phenyl alkane compound such as 2-dimethylamino-2- (4-morpholino) benzoyl-1-phenyl propane, tetra (t-butylperoxycarbonyl) benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, aminobenzene derivative such as 4, 4' -bis (diethylamino) benzophenone, 2 ' -bis (2-chlorophenyl) -4,5, 4', imidazole compounds such as 5 '-tetraphenyl-1, 2' -biimidazole (trade name "B-CIM" manufactured by Baogu chemical Co., Ltd.), halomethylated triazine compounds such as 2, 6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3, 5-triazine, 2-trichloromethyl-5- (2-benzofuran-2-yl-vinyl) -1,3,4-
Halomethyl groups such as diazoles
Oxadiazole compounds, and the like. These may be used alone in 1 kind, or more than 2 kinds may be used in combination.
The content of the photo radical polymerization initiator (E) in the resin composition of the present invention is, for example, 1 to 10 parts by weight, preferably 1 to 5 parts by weight, and particularly preferably 1.5 to 3.5 parts by weight, based on 100 parts by weight of the radical-curable compound (particularly, the polyfunctional (meth) acrylic compound (B)) contained in the resin composition. When the content of the photo radical polymerization initiator (E) is less than the above range, curing failure may be caused. On the other hand, when the content of the photo radical polymerization initiator (E) exceeds the above range, the cured product tends to be colored easily.
[ other curable Compounds ]
The resin composition of the present invention may contain a curable compound (also referred to as "other curable compound") other than the polyfunctional alicyclic epoxy compound (a) and the polyfunctional (meth) acrylic compound (B). Examples of other curable compounds include: aromatic glycidyl ether type epoxy compounds, aliphatic polyol polyglycidyl ethers, oxetane compounds (compounds having 1 or more oxetanyl groups), vinyl ether compounds (compounds having 1 or more vinyl ether groups), and the like.
The proportion of the total content of the polyfunctional alicyclic epoxy compound (a) and the polyfunctional (meth) acrylic compound (B) in the total amount (100% by weight) of the curable compounds contained in the resin composition of the present invention is, for example, 50% by weight or more, preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The upper limit of the total content of the polyfunctional alicyclic epoxy compound (a) and the polyfunctional (meth) acrylic compound (B) is 100% by weight. When the ratio of the total content of the polyfunctional alicyclic epoxy compound (a) and the polyfunctional (meth) acrylic compound (B) is less than the above range, it tends to be difficult to obtain a cured product having low curling properties, high surface hardness, and excellent scratch resistance.
[ additives ]
The resin composition of the present invention may contain various additives in addition to the above components within a range not to impair the effects of the present invention. In the present invention, it is preferable that 1 or 2 or more compounds imparting lubricity are contained, from the viewpoint that a cured product more excellent in abrasion resistance can be obtained.
Examples of the compound imparting lubricity include: silane compounds, perfluoroalkyl group-containing (meth) acrylic compounds, silyl group-containing (meth) acrylic compounds, polyether-modified (meth) acrylic compounds, silicon-modified poly (meth) acrylates, polyether-modified poly (meth) acrylates, perfluoroalkyl group-containing polyether-modified (meth) acrylates, acrylic-modified polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, perfluoroalkyl group-containing polydimethylsiloxanes, polyether-modified perfluoroalkyl group-containing polydimethylsiloxanes, and the like. The compound preferably has a reactive functional group with an epoxy group and/or a (meth) acryloyl group (the same examples as those in the surface-modified inorganic particles (C) can be mentioned).
Examples of the silane compound include: triethylsilane, t-butyldimethylsilane, and the like.
Examples of the perfluoroalkyl group-containing (meth) acrylic compound include: 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3,3, 3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, and the like.
Examples of the silyl group-containing (meth) acrylic compound include: trimethylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri (n-butyl) silyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tricyclohexylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, and the like.
The silicon-modified poly (meth) acrylate is a compound in which a silicon chain (for example, a polydimethylsiloxane chain) is bonded to a terminal and/or a side chain of a poly (meth) acrylate as a main chain.
The polyether-modified poly (meth) acrylate is a compound in which a polyether chain is bonded to a terminal and/or a side chain of a poly (meth) acrylate as a main chain.
The perfluoroalkyl group-containing poly (meth) acrylate is a compound having a perfluoroalkyl group at a terminal and/or a side chain of the poly (meth) acrylate as a main chain.
The perfluoroalkyl group-containing polyether-modified (meth) acrylate is a compound having a perfluoroalkyl group and a polyether chain at the terminal and/or side chain of poly (meth) acrylate as a main chain.
The acrylic-modified polydimethylsiloxane is a compound in which a poly (meth) acrylic chain is bonded to a terminal and/or a side chain of polydimethylsiloxane as a main chain.
The polyether-modified polydimethylsiloxane, perfluoroalkyl-containing polydimethylsiloxane, and polyether-modified perfluoroalkyl-containing polydimethylsiloxane described above are the same as those described above except that the poly (meth) acrylate is replaced with polydimethylsiloxane.
Examples of the perfluoroalkyl group include: a C3-30 perfluoroalkyl group such as perfluorooctyl group.
In the present invention, a compound containing a hydroxyl group having particularly excellent reactivity with an epoxy group of the polyfunctional alicyclic epoxy compound (A) (for example, a hydroxyl group-containing silicon-modified poly (meth) acrylate) is particularly preferably used, and the hydroxyl value is preferably, for example, 5 to 150 mgKOH/g.
The amount of the compound for imparting lubricity (in the case where 2 or more are contained, the total amount thereof) is, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and particularly preferably 0.1 to 3 parts by weight, based on the total amount (100 parts by weight) of the components (a), (B), and (C) contained in the resin composition of the present invention.
In addition, a solvent (e.g., butyl acetate, methyl ethyl ketone, etc.), a polyol, a curing aid, an organosiloxane compound, metal oxide particles, rubber particles, an antifoaming agent, a silane coupling agent, a filler, a plasticizer, a leveling agent, an antistatic agent, a release agent, a surfactant, a flame retardant, a colorant, an antioxidant, an ultraviolet absorber, an ion absorber, a phosphor, and other conventional additives can be used in the resin composition of the present invention. The content of these additives may be appropriately set, for example, within a range of 0 to 40% by weight, preferably 1 to 25% by weight, based on 100% by weight of the resin composition of the present invention.
The resin composition of the present invention can be prepared by stirring and mixing the above-mentioned respective components in a state where they are heated as necessary. The resin composition of the present invention may be used as a one-pack type composition in which a mixture of components prepared by mixing the components in advance is used as it is, or may be used as a multi-pack type (for example, a two-pack type) composition in which, for example, components divided into 2 or more parts (each component may be a mixture of 2 or more components) are mixed at a predetermined ratio before use. The stirring/mixing method is not particularly limited, and known or conventional stirring/mixing mechanisms such as various mixers including a high-speed disperser and a homogenizer, a kneader, a roll, a bead mill, and a self-rotation and revolution type stirring device can be used. In addition, defoaming may be performed under vacuum after stirring/mixing.
< composition for hard coating >
By curing the resin composition of the present invention, a cured product having low curling properties and excellent surface hardness and scratch resistance can be obtained. Therefore, the resin composition of the present invention can be preferably used as a composition for hard coating (hard coating agent).
< coated article >
The coated article can be obtained by applying the resin composition of the present invention to the surface of an article (e.g., a substrate or film made of metal or resin (e.g., plastic such as TAC or PET)) as an object (article to be coated) and curing the applied article. The coated article is excellent in both productivity and quality because the resin composition of the present invention is excellent in curability (curing rate), and the cured article of the present invention is low in curling properties and is excellent in surface hardness and scratch resistance.
The resin composition of the present invention can be cured in a very short time by irradiation with active energy rays such as ultraviolet rays or electron beams after being applied to an article. As a light source for ultraviolet irradiation, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like can be used. The irradiation time varies depending on the type of the light source, the distance between the light source and the coated surface, and other conditions, but is several tens of seconds at the longest, and usually several seconds. Generally, an irradiation source having a lamp output of about 80 to 300W/cm can be used. When electron beam irradiation is used, it is preferable to use an electron beam having an energy in the range of 50 to 1000KeV and to set the irradiation dose to 2 to 5 Mrad. After the irradiation with the active energy ray, if necessary, heating (post-curing) may be performed to promote the curing.
The resin composition of the present invention can be used in various applications such as coating agents (particularly, hard coating applications), inks, adhesives, sealants, resists, composite materials, transparent substrates, transparent films or sheets, optical materials (for example, optical lenses, etc.), optical molding die materials, electronic materials (for example, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc.), mechanical part materials, electrical part materials, automobile part materials, civil engineering and construction materials, molding materials, plastic forming materials, and solvents (for example, reactive diluents).
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
[ preparation of resin composition ]
The respective components were mixed at the blending ratios (unit: parts by weight) shown in the table, stirred by a revolution-rotation type stirring apparatus (trade name: あわとり teran AR-250, manufactured by THINKY) and defoamed to obtain resin compositions.
[ production of cured film ]
The obtained resin composition was applied to a PET substrate (trade name "LumirrorT 60", manufactured by Toray corporation; film thickness: 100. + -. 5 μm) by means of a bar coater. At this time, the coating was performed using a bar coater so that the film thickness after drying became 20 μm.
Thereafter, the mixture was dried at 80 ℃ for 1 minute, and then the mixture was placed in a nitrogen-substituted closed vessel, and the irradiation dose was about 1000mJ/cm2The conditions (3) are irradiated with ultraviolet rays, whereby curing is performed.
The laminate (cured film) having the structure of "PET substrate/cured product (cured coating film)" obtained in this way was used as a sample for evaluation of pencil hardness and scratch resistance.
Further, from the laminate (cured film) having the structure of "PET substrate/cured product (cured coating film)" obtained above, a square test piece having a side of 10cm was cut out. The film thickness at the measurement points shown by the numbers 1 to 5 circled in fig. 1(1a) was measured for the test piece. All the above-mentioned measurement points were regarded as passed when the thickness of the cured coating obtained by subtracting the thickness of the PET substrate (the thickness measured in advance) from the thickness of the measurement point was 20 μm. + -. 2 μm, and used as a curl evaluation sample. In the case of failure, the bar coater was changed until the film thickness at the measurement point reached a satisfactory level, and the coating, drying and curing steps were repeated to prepare samples for evaluation of curling properties.
Examples 2 to 10 and comparative examples 1 to 8
Resin compositions and cured products (samples) thereof were obtained in the same manner as in example 1, except that the blending amounts of the respective components were changed as shown in the table. In examples and comparative examples other than example 1 and comparative example 2, post-curing (heating at 80 ℃ for 2 hours) was performed after the irradiation with ultraviolet rays.
< evaluation >
The following evaluation tests were carried out on cured products (samples) of the resin compositions obtained in examples and comparative examples.
[ Pencil hardness ]
The pencil hardness of the cured films (the thickness of the cured coating film: about 20 μm) obtained in examples and comparative examples was measured by the following method.
The pencil hardness of the cured coating film was evaluated in accordance with JIS K5600. The evaluation was performed by visual observation, and the cured coating film on the PET substrate was scratched with a pencil, and it was considered NG (failure) that damage was observed on the surface or the substrate. Specifically, the evaluation was performed by repeating the operation of first performing the evaluation with a pencil of a certain hardness and then performing the evaluation with a pencil of a 1 st higher hardness without causing damage, and if damage is confirmed, performing the re-evaluation with a 1 st lower hardness. Further, if no damage was observed, a pencil having a hardness of 1 grade higher was used again, and when reproducibility was observed 2 times or more, the hardest pencil hardness causing no damage was taken as the pencil hardness of the cured coating film, and the evaluation result was expressed as the hardness of the pencil lead. The evaluation conditions are as follows.
Evaluation pencil: pencil for pencil hardness test manufactured by Mitsubishi Pencil (L.) Kabushiki Kaisha "
Loading: 750gf
Scratching distance: over 50mm
Scraping angle: 45 degree
And (3) measuring environment: 23 ℃ and 50% RH
The samples (cured films) used in the tests were conditioned in a constant temperature and humidity apparatus at 23 ℃ and 50% RH for 24 hours.
[ crimpability ]
With respect to the samples for evaluation of curling property obtained in examples and comparative examples, the warpage at four corners when placed on a horizontal plane as shown in fig. 1(1b) was measured, and the average value thereof was taken as the warpage amount of the cured film. The specimen having a large warpage amount is considered to have a large curing shrinkage or curing expansion. Note that, the warpage in the case where curing shrinkage occurred (the case where the surface of the cured film in contact with the horizontal plane of fig. 1(1b) was on the opposite side of the cured coating) was shown as a positive value, and the warpage in the case where curing expansion occurred (the case where the surface of the cured film in contact with the horizontal plane of fig. 1(1b) was on the cured coating side) was shown as a negative value.
[ scratch resistance ]
The cured films (film thickness about 20 μm) obtained in examples and comparative examples were coated with steel wool #0000 at a coating surface weight of 500g/cm2Or 1kg/cm2The load of (2) was subjected to friction of 20 reciprocating motions, 200 reciprocating motions, and 1000 reciprocating motions, and the abrasion resistance was evaluated. The scratch resistance was evaluated as follows.
A: no damage after 1000 reciprocating
B: no damage after 200 reciprocating and micro damage after 1000 reciprocating
C: has no injury after 200 reciprocating, and slight injury or slight turbidity after 1000 reciprocating
D: no damage after 200 reciprocating, obvious damage or obvious turbidity after 1000 reciprocating
E: no damage after 20 reciprocating and micro damage after 200 reciprocating
F: has no injury after 20 reciprocating cycles, and has slight injury or slight turbidity after 200 reciprocating cycles
G: no damage after 20 reciprocating cycles, obvious damage or obvious turbidity after 200 reciprocating cycles
H: after 20 reciprocating, the micro-damage exists
I: after 20 cycles, there was mild injury or mild turbidity
[ Table 1]
[ Table 2]
The abbreviations in tables 1 and 2 represent the following compounds.
NANOPOX C620: a compound obtained by reacting CELLOXIDE2021P (60 parts by weight) with hydroxyl group-containing silica (silica average particle diameter: 10nm) (40 parts by weight), trade name "NANOPOX C620", manufactured by EVONIC
Y10C-JFS: a mixture of CELLOXIDE2021P (80.5 parts by weight) and alicyclic epoxy group-containing silica (average silica particle diameter: 10nm) (19.5 parts by weight) was sold under the trade name "Y10C-JFS", manufactured by Admatechs
Celloxin 2021P: 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, trade name "CELLOXIDE 2021P", manufactured by Daicel
A-9550: dipentaerythritol polyacrylate, molecular weight of about 554, hydroxyl value of about 56mgKOH/g, manufactured by Ninghamu chemical Co., Ltd
A-TMM-3L-N: pentaerythritol triacrylate, molecular weight 246, hydroxyl value of about 112mgKOH/g, manufactured by Ninghamu chemical Co., Ltd
DPHA: dipentaerythritol hexaacrylate, molecular weight: 578, "DPHA", manufactured by Daicel-Allnex
Y10C-MFK: methyl ethyl ketone dispersion (silica concentration: 30% by weight) of glycidyl ether group-containing silica (silica average particle diameter: 10nm), trade name "Y10C-MFK", manufactured by Admatechs
CPI-210S: diphenyl [4- (phenylthio) phenyl ] sulfonium tris (pentafluoroethyl) trifluorophosphate, trade name "CPI-210S", SAN-APRO (strain)
Irgacure 184: 1-hydroxycyclohexyl phenyl ketones
BYK-SILCLEAN 3700: a hydroxyl group-containing silicon-modified polyacrylate having a hydroxyl value of about 30mgKOH/g, a trade name of BYK-SILCLEAN 3700, manufactured by BYK Chemie Japan
Industrial applicability
By irradiating the resin composition for forming a hard coat layer of the present invention with active energy rays, a cured product having high surface hardness, excellent scratch resistance, and low curling properties can be formed, and the resin composition can be suitably used for applications in which a hard coat layer is formed on the surface of a plastic film or a glass substrate.
Description of the symbols
1 cured film
2 horizontal plane
3 amount of warp
Claims (7)
1. A resin composition for forming a hard coat layer, comprising:
a polyfunctional alicyclic epoxy compound (A) having an alicyclic structure and 2 or more epoxy groups in 1 molecule,
A polyfunctional acrylic compound or methacrylic compound (B) having 2 or more acryloyl groups or methacryloyl groups in 1 molecule,
Surface-modified inorganic particles (C) having an inorganic particle surface with an average particle diameter of 0.1 to 100nm as measured by a dynamic light scattering method and a reactive functional group with an epoxy group, an acryloyl group and/or a methacryloyl group,
Photo cation polymerization initiator (D), and
a photo radical polymerization initiator (E),
wherein the polyfunctional alicyclic epoxy compound (A) is a compound represented by the following formula (I):
wherein X represents a single bond or a linking group selected from: a linear or branched alkylene group or a divalent alicyclic hydrocarbon group having 1 to 18 carbon atoms, a linear or branched alkenylene group having 2 to 8 carbon atoms wherein part or all of the carbon-carbon double bonds have been epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a group formed by connecting a plurality of the above groups, and 1 or more of the carbon atoms constituting the cyclohexane ring in the formula (I) being optionally substituted with an alkyl group;
the content of the (A) is 3 to 35 wt% of the sum (100 wt%) of the contents of the (A) and the (B).
2. The resin composition for forming a hard coat layer according to claim 1, wherein the content of (C) is 5 to 40 parts by weight with respect to 100 parts by weight of the total content of (A) and (B).
3. The resin composition for forming a hard coat layer according to claim 1 or 2, wherein the total concentration of the acryloyl group and the methacryloyl group in the total amount of (a), (B), and (C) contained in the resin composition for forming a hard coat layer is more than 5.0 mmol/g.
4. The resin composition for forming a hard coat layer according to claim 1 or 2, wherein the inorganic particles in the surface-modified inorganic particles (C) are silica.
5. The resin composition for forming a hard coat layer according to claim 1 or 2, further comprising at least one compound having a reactive functional group with an epoxy group, an acryloyl group and/or a methacryloyl group selected from the group consisting of:
silicon compounds, perfluoroalkyl-containing acrylic compounds, perfluoroalkyl-containing methacrylic compounds, silyl-containing acrylic compounds, silyl-containing methacrylic compounds, polyether-modified acrylic compounds, polyether-modified methacrylic compounds, silicon-modified polyacrylates, silicon-modified polymethacrylates, polyether-modified polyacrylates, polyether-modified polymethacrylates, perfluoroalkyl-containing polyacrylates, perfluoroalkyl-containing polymethacrylates, perfluoroalkyl-containing polyether-modified acrylates, perfluoroalkyl-containing polyether-modified methacrylates, acrylic-modified polydimethylsiloxanes, polyether-modified polydimethylsiloxanes, perfluoroalkyl-containing polydimethylsiloxanes, and polyether-modified perfluoroalkyl-containing polydimethylsiloxanes.
6. A cured product of the resin composition for forming a hard coat layer according to any one of claims 1 to 5.
7. A coated article having a hard coat layer formed on the surface of an article, the hard coat layer being formed from a cured product of the resin composition for forming a hard coat layer according to any one of claims 1 to 5.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015086412 | 2015-04-21 | ||
| JP2015-086412 | 2015-04-21 | ||
| PCT/JP2016/061718 WO2016171024A1 (en) | 2015-04-21 | 2016-04-11 | Hard coat layer-forming resin composition and cured product thereof |
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| CN107406690A CN107406690A (en) | 2017-11-28 |
| CN107406690B true CN107406690B (en) | 2020-06-09 |
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| JP (1) | JP6147947B2 (en) |
| CN (1) | CN107406690B (en) |
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| WO (1) | WO2016171024A1 (en) |
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| JP6729684B2 (en) * | 2016-04-18 | 2020-07-22 | Jnc株式会社 | Thermosetting resin composition, cured film, substrate with cured film, and electronic component |
| JP6885406B2 (en) * | 2016-08-26 | 2021-06-16 | Jnc株式会社 | Epoxy resin composition and low-curing shrinkable resin cured film with excellent adhesion |
| WO2019026460A1 (en) * | 2017-08-04 | 2019-02-07 | 株式会社ダイセル | Resin composition for forming hard coating layer |
| KR20200052948A (en) * | 2017-09-15 | 2020-05-15 | 스미또모 가가꾸 가부시키가이샤 | Curable composition |
| US20200347180A1 (en) * | 2018-01-24 | 2020-11-05 | Daicel Corporation | Resin composition for forming hard coating layer |
| US11827796B2 (en) | 2018-04-16 | 2023-11-28 | Canon Kabushiki Kaisha | Curable resin composition for three-dimensional shaping and method of manufacturing three-dimensionally shaped product |
| CN111936904B (en) | 2018-04-16 | 2023-02-21 | 住友电气工业株式会社 | Optical fiber |
| EP3835377B1 (en) * | 2018-08-08 | 2023-10-18 | Mitsubishi Gas Chemical Company, Inc. | Hard-coat composition, laminate film, and curable film |
| JP7327405B2 (en) | 2018-08-22 | 2023-08-16 | 住友電気工業株式会社 | optical fiber |
| CN116948523B (en) * | 2023-02-03 | 2024-05-03 | 北京驳凡科技有限公司 | UV resin composition and application thereof |
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| JP4055427B2 (en) * | 2001-02-23 | 2008-03-05 | 富士フイルム株式会社 | CURABLE COMPOSITION, HARD COAT TREATED ARTICLE USING THE SAME, AND IMAGE DISPLAY DEVICE |
| JP2004141732A (en) * | 2002-10-23 | 2004-05-20 | Fuji Photo Film Co Ltd | Curable composition, article hard-coated by using the same and picture display device |
| JP5483810B2 (en) * | 2007-09-28 | 2014-05-07 | 株式会社ニデック | Resin composition |
| JP5540495B2 (en) * | 2008-11-17 | 2014-07-02 | 大日本印刷株式会社 | Curable resin composition for hard coat layer and hard coat film |
| JPWO2014069231A1 (en) * | 2012-10-31 | 2016-09-08 | 株式会社ダイセル | Radiation curable composition, adhesive, and polarizing plate |
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| JP6147947B2 (en) | 2017-06-14 |
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| WO2016171024A1 (en) | 2016-10-27 |
| JPWO2016171024A1 (en) | 2017-08-31 |
| TW201700650A (en) | 2017-01-01 |
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