JP2011039165A - Alkali-soluble photocurable composition, cured coating film using the composition and transparent member - Google Patents

Alkali-soluble photocurable composition, cured coating film using the composition and transparent member Download PDF

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JP2011039165A
JP2011039165A JP2009184710A JP2009184710A JP2011039165A JP 2011039165 A JP2011039165 A JP 2011039165A JP 2009184710 A JP2009184710 A JP 2009184710A JP 2009184710 A JP2009184710 A JP 2009184710A JP 2011039165 A JP2011039165 A JP 2011039165A
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photocurable composition
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acrylate
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Seiji Haruhara
Megumi Tomomatsu
Masayuki Wada
恵 友松
真幸 和田
聖司 春原
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Hitachi Chem Co Ltd
日立化成工業株式会社
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Abstract

The present invention provides a composition that can be applied as a transparent member desired in the field of display devices such as liquid crystal displays and touch panels, or the field of organic TFTs, and can be developed with an alkaline aqueous solution. To provide a photocurable composition having high hardness and having excellent adhesion to substrates such as glass, metal oxide and metal.
(A) An alkali-soluble resin which is a (meth) acrylate copolymer having a carboxyl group and an ethylenically unsaturated group in the molecule, (B) silica fine particles, and (C) one in a single molecule. A reactive monomer having the above (meth) acryloyl group, comprising (C1) a (meth) acrylate compound having a fluorene skeleton, and (C2) a (meth) acrylate compound having an alkoxysilane moiety; (D) A photocurable composition comprising a photopolymerization initiator is prepared and used.
[Selection] Figure 1

Description

  The present invention is a light that can be developed with an alkaline aqueous solution, the prepared coating film has low water absorption and high hardness, and has high adhesion to substrates such as glass, metal oxide, and metal. The present invention relates to a curable composition. Since the photocurable composition of the present invention has low water absorption and high hardness and is excellent in adhesion to a substrate, it is a transparent member for forming an interlayer insulating film used in the field of various display devices such as liquid crystal displays and other touch panels. The present invention can be applied to a transparent member used in the field of organic TFT (thin film transistor).

  The development in the information society is remarkable, and with the diversification and speeding up of information, in recent years, necessary information can be easily obtained. The development in the information society has greatly contributed to the rapid progress and popularization of personal computers. However, as the application range of personal computers gradually expands, it has become difficult to provide sufficient customer satisfaction with input using a keyboard or a mouse as in the related art regarding interface input device technology.

  Under such circumstances, a touch panel that can be carried around, can be easily operated, and can input handwritten characters has recently attracted attention as an interface device. As a touch panel method, a resistance film method, an optical method, a capacitance method, an ultrasonic method, a pressure method, and the like are typically known, and a resistive film type touch panel is mainly used in the current market. (See Non-Patent Document 1).

  In many cases, the touch panel is subjected to pressure from the outside. Therefore, the constituent material has a hardness capable of withstanding an impact, and needs to have a high transmittance in order to prevent deterioration in display quality. However, resistance film type touch panels tend to have low durability against external pressure or the like, for example, received during input. Therefore, in recent years, there has been an increasing demand for capacitive touch panels having excellent display quality due to excellent reliability such as input durability and high transmittance, and various studies have been conducted (patents). Reference 1).

A capacitive touch panel is typically disposed on a first transparent electrode such as ITO (Indium Tin Oxide) provided on a substrate, an insulating film such as SiO 2, and the like, and A second transparent electrode electrically connected to the first transparent electrode; In the touch panel having such a structure, adhesion between the layers is important. In addition, in order to form a contact hole for conducting the first transparent electrode and the second transparent electrode, a material constituting the insulating film is required to have high resolution. Furthermore, in the technical field of patterning an insulating film or the like, development with an alkaline aqueous solution is generally preferable. Therefore, as the material, a material that can be developed with an alkaline aqueous solution is desired.

  Patent Documents 2 to 4 are curable products obtained by using a silane compound as a composition having excellent transparency and high hardness and uniformly dispersing the colloidal silica in a radical polymerizable vinyl compound such as methacrylate. A composition is disclosed.

JP 2009-3518 A JP-A-5-209027 JP-A-10-231339 JP 10-298252 A

Resistive transparent touch panel Fujikura Technical Report (2002)

  However, since all the compositions disclosed in Patent Documents 2 to 4 are compositions that do not dissolve in an alkaline aqueous solution, development with an alkaline aqueous solution is difficult. Therefore, the present invention can be developed with an aqueous alkali solution, the prepared coating film has low water absorption and high hardness, and has excellent adhesion to substrates such as glass, metal oxides, and metals, An object is to provide a photocurable composition, a cured coating film using the composition, and a transparent member.

  As a result of intensive studies to solve the problems in view of the above-described conventional techniques, the present inventors dispersed silica fine particles in a component containing a specific (meth) acrylate compound and cured them with light or the like. To achieve a photocurable composition having low water absorption and high hardness and having excellent adhesion to substrates such as glass, metal oxides and metals, and to complete the present invention. It came. That is, the features of the present invention relate to the items described below.

  The first of the present invention is (A) an alkali-soluble resin which is a (meth) acrylate copolymer having a carboxyl group and an ethylenically unsaturated group in the molecule, (B) silica fine particles, and (C) a single molecule. A reactive monomer having one or more (meth) acryloyl groups therein, (C1) a (meth) acrylate compound having a fluorene skeleton, and (C2) a (meth) acrylate compound having an alkoxysilane moiety The present invention relates to a photocurable composition comprising a monomer and (D) a photopolymerization initiator.

  Here, it is preferable that the said photocurable composition further contains a polyfunctional epoxy compound as (E) component. Moreover, it is preferable that an organic solvent is further included as (F) component.

  The component (C1) is a di (meth) acrylate compound represented by the following general formula (1), and the component (C2) is preferably a mono (meth) acrylate compound represented by the following general formula (2). .

[Wherein, two R 1 s each independently represent a hydrogen atom or a methyl group, and two R 2 s each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, Each R 3 independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and m is an integer of 0 to 10].

[Wherein R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrocarbon group having 1 to 10 carbon atoms, R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents It is an integer of 1-6, r is an integer of 0-2]

Moreover, it is preferable that the said (E) polyfunctional epoxy compound is a compound shown by following General formula (3).

[Wherein, R 7 , R 8 and R 9 each independently represent a hydrogen atom or a methyl group, but all of R 7 , R 8 and R 9 are not simultaneously hydrogen atoms]

  As the (F) organic solvent, it is preferable to use at least one ether solvent having a boiling point of 120 to 250 ° C. at 750 mmHg.

  2nd of this invention is related with the cured coating film obtained by irradiating the photocurable composition by this invention with actinic light. The cured coating film according to the present invention is preferably used as a transparent member for a touch panel, a transparent member for a liquid crystal display, or a transparent member for an organic thin film transistor.

  According to the present invention, development is possible with an alkaline aqueous solution, the prepared coating film has low water absorption and high hardness, and further has high adhesion to substrates such as glass, metal oxides, and metals. A photocurable composition can be provided. The composition has the above various properties and is easily cured by active energy rays to form a good coating film. Therefore, it is extremely useful as a transparent member for forming an interlayer insulating film in the field of various display devices such as liquid crystal displays and other touch panels, or as a transparent member used in the field of organic TFTs.

FIG. 1 is a schematic cross-sectional view showing an embodiment of a touch panel using a cured coating film of a photocurable composition according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail.
<Photocurable composition>
The photocurable composition according to the present invention comprises (A) an alkali-soluble resin which is a (meth) acrylate copolymer having a carboxyl group and an ethylenically unsaturated group in the molecule, (B) silica fine particles, (C) a single It contains two specific components that are reactive monomers having one or more (meth) acryloyl groups in the molecule, and (D) a photopolymerization initiator. Here, the “photo-curing type” means that a reaction occurs between each component by irradiation of energy rays such as an electron beam and a light beam, and the composition can be cured. Hereinafter, each component which comprises the said photocurable composition is demonstrated.

(A) Alkali-soluble resin The alkali-soluble resin (A) used in the present invention is a (meth) acrylate copolymer having a carboxyl group and an ethylenically unsaturated group in the molecule. Here, (meth) acrylate means acrylate or methacrylate. In such a (meth) acrylate copolymer, the carboxyl group provides solubility in an alkaline aqueous solution, and the ethylenically unsaturated group provides curability to light or heat. The copolymer preferably has two or more ethylenically unsaturated groups in one molecule from the viewpoint of curability. Specific examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth) acryloyl group. Among them, a (meth) acryloyl group is preferable because of good reactivity.

  The (meth) acrylate copolymer used as the alkali-soluble resin (A) has a carboxyl group by first using (1) a (meth) acrylate having a carboxyl group and the other first polymerizable compound. In order to introduce an ethylenically unsaturated group as a side chain into a part of the carboxyl group in the copolymer obtained in (2) above (1), and then the step of producing a (meth) acrylate copolymer, the carboxyl group The second polymerizable compound having a functional group that reacts with can be produced by a method including a step of reacting with the copolymer. Hereinafter, although the manufacturing method of the said (meth) acrylate copolymer is demonstrated more concretely, a manufacturing method is not restrict | limited to them.

  In the method for producing the (meth) acrylate copolymer, in the step (1), the use of a (meth) acrylate having a carboxyl group is essential, and other various polymerizable compounds are used to constitute the copolymer. can do. Although it does not specifically limit, As a specific example of the (meth) acrylate which has a carboxyl group which can be used by this invention, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acrylic acid And leuoxyethyl hexahydrophthalic acid.

  Specific examples of the first polymerizable compound that can be used in combination with the (meth) acrylate having a carboxyl group include various aliphatic, alicyclic and aromatic (meth) acrylates. However, the first polymerizable compound is not limited to a (meth) acryloyl group-containing compound, and may be a monomer compound containing another ethylenically unsaturated group such as a vinyl group. For example, aromatic vinyl compounds such as styrene and α-methylstyrene can be used as the first polymerizable compound. Moreover, the monomer compound of the cyclic structure containing ethylenically unsaturated groups, such as maleimide, can be used. Hereinafter, various monomer compounds that can be used as the first polymerizable compound will be described as specific examples.

  Specific examples of the aliphatic (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl ( Carbon number of alkyl groups such as (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, alkyl (meth) acrylate having alkyl group of alkyl chain C12-C15, n-stearyl (meth) acrylate, etc. 1-20 alkyl (meth) acrylate, n-butoxyethyl (meth) acrylate, etc., C1-C20 alkoxyalkyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethyleneglycol Le (meth) acrylate, methoxy polyethylene glycol (meth) acrylate alkoxy (poly) alkylene glycol (meth) acrylate.

  Specific examples of the aromatic (meth) acrylate include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

  Furthermore, specific examples of the alicyclic (meth) acrylate include a cyclic monomer having a cyclo ring and an ethylenically unsaturated bond. They are cyclic monomers such as cyclopentenyl (meth) acrylate, where the cyclo ring is a cycloalkane ring, and cyclo rings such as dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate are cycloalkene rings. It may be a cyclic monomer.

  Another example of the alicyclic (meth) acrylate is a cyclic monomer having a bicyclo ring and an ethylenically unsaturated bond. More specifically, a cyclic monomer (bornyl (meth)) having a bornyl group (endo-1,7,7-trimethylbicyclo [2.2.1] hept-2-yl group) and a (meth) acryloyl group. Acrylate, etc.), cyclic monomers (isobornyl (meth) acrylate, etc.) having an isobornyl group (exo-1,7,7-trimethylbicyclo [2.2.1] hept-2-yl group) and a (meth) acryloyl group ) And the like.

Furthermore, another example of the alicyclic (meth) acrylate includes a cyclic monomer having a tricyclo ring and an ethylenically unsaturated bond. More specifically, as a tricyclo group, a tricyclo [5.2.1.0 2,6 ] decanyl group obtained by removing one hydrogen atom from tricyclo [5.2.1.0 2,6 ] decane, Tricyclo [5.1.0 2,6 ] -3-decene (tricyclo [5.2.1.0 2,6 ] -dec-3-ene) in which one hydrogen atom is removed. 2.1.0 2,6 ] -3-decenyl group (also referred to as dicyclopentenyl group) and a cyclic monomer having a (meth) acryloyl group as an ethylenically unsaturated bond.

Here, the above-exemplified tricyclo group and (meth) acryloyl group are preferably bonded via —O— or —O—R—O— (R is an alkylene group). Specific examples of the cyclic monomer having a tricyclo ring and an ethylenically unsaturated bond include the following compounds.
Acryloyloxytricyclo [5.2.1.0 2,6 ] decane (manufactured by Hitachi Chemical Co., Ltd., FANCYL FA-513A), methacryloyloxytricyclo [5.2.1.0 2,6 ] decane (Hitachi Chemical) (Meth) acryloyloxytricyclo [5.2.1.0 2,6 ] decane such as FANCYL FA-513M, manufactured by Kogyo Co., Ltd.
(Meth) acryloyloxytricyclo [5.2.1] such as acryloyloxytricyclo [5.2.1.0 2,6 ] -dec-3-ene (manufactured by Hitachi Chemical Co., Ltd., FANCYL FA-511A). .0 2,6] - dec-3-ene.
(Meth) acryloyloxyalkyloxytricyclo [5.2, such as acryloyloxyethyloxytricyclo [5.2.1.0 2,6 ] -3-decene (manufactured by Hitachi Chemical Co., Ltd., FANCYL FA-512A). 1.0 2,6 ] -dec-3-ene.

  Specific examples of the compound having the maleimide structure include N-hydroxymaleimide such as N-methylmaleimide, N-ethylmaleimide and N-propylmaleimide, N-hydroxymaleimide such as N-hydroxymethylmaleimide and N-1-hydroxyethylmaleimide. Alkylmaleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-2-chlorocyclohexylmaleimide and other cycloalkylmaleimide, N-phenylmaleimide, N-2-methylphenylmaleimide N-arylmaleimides such as N-2-ethylphenylmaleimide and N-2-chlorophenylmaleimide. Although not particularly limited, among the exemplified examples, N-cycloalkylmaleimide is preferably used from the viewpoint of transparency and solubility, and N-cyclohexylmaleimide and N-2-methylcyclohexylmaleimide may be used. Further preferred. These compounds may be used alone or in combination of two or more. When using the compound which has a maleimide structure, it is preferable to use in 3-50 mass% with respect to the total mass of all the monomer components used in the said process (1).

  In the present invention, the (meth) acrylate copolymer produced in the above step (1) requires a carboxyl group, and a part thereof is used as a reactive site for introducing an unsaturated group in the step (2). . In order to form such a reactive site, the (meth) acrylate copolymer has other functional groups such as a hydroxyl group that can introduce a side chain, if necessary, in addition to a carboxyl group. May be. In order to produce such a copolymer, in the step (1), as the first polymerizable compound, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- A (meth) acrylate having a hydroxyl group such as hydroxybutyl (meth) acrylate can be used. The (meth) acrylate having a functional group such as a hydroxyl group capable of introducing a side chain may be used in the range of 0 to 30% by mass with respect to the total mass of all monomer components used in the step (1). preferable.

  Although it does not specifically limit, in one Embodiment of this invention, the (meth) acrylate copolymer manufactured at the said process (1) is the (meth) acrylate which has a carboxyl group, aliphatic, aromatic, and fat. A cyclic (meth) acrylate, a (meth) acrylate having a hydroxyl group, and at least one first polymerizable compound selected from the group consisting of compounds having an ethylenically unsaturated group other than a (meth) acryloyl group Obtained by polymerization. In this invention, it is possible to adjust the solubility of the resin at the time of image development by aqueous alkali solution by adjusting appropriately the usage-amount of the (meth) acrylate which has the said carboxyl group.

  In one embodiment of the present invention, the (meth) acrylate having a carboxyl group is preferably 1 to 50% by mass, more preferably based on the total mass of monomer components used to produce the copolymer. It can be used in the range of 5 to 45% by mass, particularly preferably 7 to 45% by mass. By making the mass ratio of the (meth) acrylate having a carboxyl group to the mass of all monomer components 1% by mass or more, the developability with respect to the alkaline aqueous solution can be improved. On the other hand, by setting the polymerization ratio to 50% by mass or less, it is possible to suppress problems such as a pattern flowing due to excessively high solubility of the resin in an alkaline aqueous solution during development, and a fine pattern can be formed. . The mass ratio of the above-mentioned carboxyl group-containing (meth) acrylate in all monomer components is preferably adjusted appropriately depending on the concentration of the alkaline aqueous solution, but generally the concentration of the alkaline aqueous solution used during development is considered. Then, it is especially preferable that the mass ratio of the (meth) acrylate having a carboxyl group is in the range of 7 to 45% by mass.

  The aliphatic (meth) acrylate, aromatic (meth) acrylate and alicyclic (meth) acrylate used as the first polymerizable compound are added to the total mass of the monomer components used to produce the copolymer. On the other hand, it is preferably used at a ratio of 10 to 90% by mass. Although it does not specifically limit, when an alicyclic (meth) acrylate is used among said various (meth) acrylates, it is preferable at the point from which characteristics, such as transparency, become more favorable. Moreover, when using the monomer compound which has a maleimide structure as said 1st polymeric compound, it is preferable to use in 3-50 mass% with respect to the total mass of a monomer component. Moreover, when using the (meth) acrylate which has a hydroxyl group as said 1st polymeric compound, it is preferable to use in 0-30 mass% with respect to the total mass of a monomer component. Furthermore, when using other monomer components, for example, styrene or α-methylstyrene, it can be adjusted within the range of the remaining mass of each of the monomer components.

  After the step (1), the obtained copolymer has a functional group capable of undergoing an addition reaction with respect to a carboxyl group in the copolymer or a functional group such as a hydroxyl group introduced as necessary. In addition, an ethylenically unsaturated group can be introduced into the copolymer by reacting with a second polymerizable compound having an ethylenically unsaturated group. Although it does not specifically limit, an isocyanate group and an epoxy group are mentioned as a specific example of the functional group in the said 2nd polymeric compound. Specific examples of the isocyanate group-containing compound that can be used as the second polymerizable compound in the present invention include 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and the like. Is mentioned. Moreover, glycidyl (meth) acrylate is mentioned as a specific example of an epoxy group containing compound.

  The amount of the second polymerizable compound added to the (meth) acrylate copolymer having a carboxyl group obtained by the step (1) is preferably 0.01 to 5.0 mmol / g, more preferably 0.00. The range is from 05 to 4.5 mmol / g, particularly preferably from 0.1 to 4.0 mmol / g. By adjusting the addition amount of the second polymerizable compound within the above range, the copolymer used as the component (A) is imparted with an appropriate reactivity to achieve the desired effect in the present invention. Can do.

(B) Silica fine particles The silica fine particles used in the present invention are not particularly limited as long as they are metal oxides containing silicon. However, if the particle size of the silica fine particles is too small, the dispersibility is lowered, whereas if it is too large, the transmittance tends to be reduced. In one embodiment of the present invention, the average particle size of the silica fine particles used is preferably 1 to 500 nm, more preferably 1 to 300 nm, and particularly preferably 1 nm to 200 nm. By using silica fine particles having a particle size in this range, it is possible to suppress a decrease in dispersion stability and transmittance. In addition, the said average particle diameter can be measured using a laser diffraction type particle size distribution measuring apparatus, for example.

  The addition amount of the silica fine particles is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and more preferably 10 to 40% by mass based on the mass of all solid components (components excluding the organic solvent) in the photocurable composition. % Is particularly preferred. By using the silica fine particles in an addition amount within the above range, it becomes easy to provide a coating film having sufficient hardness. Moreover, it is easy to maintain the excellent dispersibility and storage stability of the photocurable composition.

  The silica fine particles used in the present invention may be dried powdery silica fine particles or colloidal silica dispersed in an organic solvent. In order to obtain the dispersion stability of the composition, it is preferable to use the colloidal silica. The organic solvent used to form the colloidal silica may be an organic solvent that can dissolve organic components such as resins and polymers contained in the photocurable composition, and can disperse the colloidal silica well. There is no particular limitation. You may mix and use several types of organic solvents.

  As an example of an organic solvent for forming the colloidal silica, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and other diethylene glycol mono- or dialkyl ethers, diethylene glycol monomethyl ether acetate, diethylene glycol Acetylates of diethylene glycol monoalkyl ethers such as ethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, Triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Nopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and other propylene glycol mono or dialkyl ethers, propylene glycol monomethyl ether acetate, Examples include acetylated products of propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate, and lactones such as β-lactone, γ-lactone and δ-lactone.

(C) Reactive monomer (C) A reactive monomer having one or more (meth) acryloyl groups in a single molecule used in the present invention has (C1) a fluorene skeleton from the viewpoint of adhesion and the like (meta ) Acrylate compound and (C2) (meth) acrylate compound having an alkoxysilane moiety are essential components. The component (C1) is preferably a di (meth) acrylate compound represented by the following general formula (1), and the component (C2) has an alkoxysilane moiety in the molecule represented by the following general formula (2). Mono (meth) acrylate compounds are preferred.
In the present invention, as the reactive monomer (C), in addition to the components (C1) and (C2), as the component (C3), in addition to the above (C1), from the viewpoint of hygroscopicity and adhesion, molecules It is preferable to use a (meth) acrylate compound having two or more ethylenically unsaturated groups therein. Hereinafter, each component will be described.

Ingredient (C1)
The component (C1) is a (meth) acrylate compound having a fluorene skeleton, but specifically, it is preferably a di (meth) acrylate compound represented by the following general formula (1).

In the above formula, two R 1 s each independently represent a hydrogen atom or a methyl group, and two R 2 s each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, R 3 each independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and m is an integer of 0 to 10. More specifically, the divalent hydrocarbon group having 1 to 20 carbon atoms in R 2 and R 3 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or Examples thereof include an alkynylene group, a cycloalkylene group having 5 to 12 carbon atoms, an arylene group having 6 to 14 carbon atoms, and an aralkylene group having 7 to 20 carbon atoms.

Specific examples of the compound that can be used as the component (C1) in the present invention include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy). Phenyl] fluorene, a compound in which a plurality of ethoxy moieties of the above compounds are repeated (that is,-(OR 3 ) m- in the general formula (I) is-(OC 2 H 4 ) m-, and m is 1 or more. As well as those in which the ethoxy moiety is repeated one or more times as a propoxy group (ie R 2 is —C 2 H 3 (CH 3 ) —), and — (OR 3 ) of the general formula (I) ) M- is — (OC 2 H 3 (CH 3 )) m—, and m is 0 or more). Among these, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene are preferable.

Ingredient (C2)
Component (C2) is preferably a mono (meth) acrylate compound having an alkoxysilane moiety in the molecule represented by the following general formula (2).

In the above formula, R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrocarbon group having 1 to 10 carbon atoms (preferably an alkyl group or phenyl group having 1 to 3 carbon atoms), and R 6 represents a hydrogen atom. Or a C1-C10 hydrocarbon group (preferably a C1-C3 alkyl group or a phenyl group) is represented, n is an integer of 1-6, r represents the integer of 0-2.

  Specific examples of compounds that can be used as component (C2) in the present invention include γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldiethylmethoxysilane, and γ-acryloxypropylethyldimethoxy. Silane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxypropyldiethylethoxysilane, γ-acryloxypropylethyldiethoxysilane, γ -Acryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldiethylmethoxysilane , Γ-methacryloxypropylethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldiethylethoxysilane, γ- Examples include methacryloxypropylethyldiethoxysilane and γ-methacryloxypropyltriethoxysilane.

  Although not particularly limited, from the viewpoint of fluidity reduction and thermal stability of the photocurable composition, preferred compounds are γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ- Examples include methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

Ingredient (C3)
In the present invention, the reactive monomer (C) has, in addition to the above components (C1) and (C2), (C3) having two or more unsaturated groups in the molecule which are different from those components (meth). It is preferable to use an acrylate compound. As described above, the reactive monomer (C) can further improve adhesion and the like by including the component (C3).
In the present invention, the component (C3) is not particularly limited as long as it is a (meth) acrylate compound having two or more unsaturated groups in the molecule. Specific examples of compounds that can be used as component (C3) in the present invention include EO (ethylene oxide) modified bisphenol A diacrylate, ECH modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1, 3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO modified phosphoric acid diacrylate, ECH (epichlorohydrin) modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, Tetraethylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, trimethylol group Pan triacrylate, pentaerythritol triacrylate, EO-modified phosphoric acid triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (PO means propylene oxide, the same applies hereinafter), pentaerythritol tetraacrylate, di Examples thereof include acrylates such as pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate, and methacrylates corresponding thereto.

  Although not particularly limited, among the compounds exemplified above, di (meth) acrylate compounds such as EO-modified bisphenol A diacrylate and EO-modified bisphenol A dimethacrylate are preferable in terms of adhesion and the like.

  When the reactive monomer (C) is composed of the components (C1), (C2) and (C3), various properties such as adhesion and hardness of the coating film can be obtained by blending each component in an appropriate ratio. The balance can be improved. In one embodiment of the present invention, the proportion of the components (C1) to (C3) in the photocurable composition is preferably (C1) of 5 to 25 masses based on the mass of all solid components in the composition. %, Particularly preferably in the range of 10-25% by mass, (C2) is preferably in the range of 1-15% by mass, particularly preferably in the range of 3-15% by mass, and (C3) is preferably in the range of 5-25% by mass. %, Particularly preferably in the range of 10 to 25% by mass. By making the amount of component (C1) used 5% by mass or more, it becomes easy to increase the hardness of the coating film, and by making it 25% by mass or less, both properties such as hardness and adhesion of the coating film are well balanced. It becomes easy to provide. By making the amount of the component (C2) used 1% by mass or more, it becomes easy to favorably disperse the silica in the system, and by making it 15% by mass or less, it is easy to maintain good compatibility with the organic solvent. Become. By making (C3) 5% by mass or more, it becomes easy to provide a coating film having sufficient hardness, and by making it 25% by mass or less, it is possible to provide a coating film having sufficient adhesion. It becomes easy.

(D) Photopolymerization initiator The photopolymerization initiator used in the present invention may be a compound that generates active species such as radicals by light irradiation and promotes polymerization. In the examples of the present invention, a photopolymerization initiator that causes a photoradical reaction by i-line (wavelength: 365 nm) was studied, but the type of the photopolymerization initiator is not particularly limited, and depends on the wavelength to be applied. An appropriate compound can be appropriately selected from known compounds as a photopolymerization initiator.

  Examples of the photopolymerization initiator that can be used in the present invention include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzyl, and 2,2-diethoxyacetophenone. , Benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphtho Non, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 1, 2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethane, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ]-, 1- (O-acetyloxime). These photoinitiators can be used individually or in combination of 2 or more types.

  The content of the photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.5 to 8% by mass, based on the mass of all solid components in the photocurable composition, and 0.1 to 7%. Mass% is particularly preferred. By making content of a photoinitiator into the said range, it is easy to raise the photosensitivity of a composition and to accelerate | stimulate reaction. In addition, problems such as a decrease in transparency and the resulting pattern breakage, and the occurrence of development residue in unexposed areas are less likely to occur.

(E) Multivalent epoxy compound In the present invention, in order to further improve the adhesion and the like, it is preferable to use a polyvalent epoxy compound having two or more epoxy groups in the molecule. Such a polyvalent epoxy compound is preferably a monomer compound having two or more epoxy groups having a methyl group at the β-position in the molecule, and is a diepoxy compound having two such epoxy groups. More preferred. It preferably contains a compound represented by the following general formula (3).

In the general formula (3), R 7 , R 8 and R 9 are each independently a hydrogen atom or a methyl group. However, all of R 7 , R 8 and R 9 are not hydrogen atoms. As an example of a specific compound represented by the above general formula (3), 1,2: 8,9 diepoxy limonene (manufactured by Daicel Chemical Industries, trade name “Celoxide 3000”) may be mentioned, which is preferably used in the present invention. can do.

  The ratio of the diepoxy monomer when the photocurable composition is cured to form a coating film is preferably 1 to 30% by mass, particularly preferably 3 to 20% by mass. When the ratio of the diepoxy monomer is less than 1% by mass based on the mass of all solid components in the photocurable composition, a decrease in hygroscopicity may be observed, and when it is more than 30% by mass, storage stability may be observed. May adversely affect sex. When mixed in the above range, it was clear that the hygroscopic decrease and the effect on storage stability were reduced.

(F) Organic solvent In the present invention, an organic solvent is generally used to dissolve or disperse each component. The type is not particularly limited, but from the viewpoint of development characteristics and the like, it is preferable to use at least one ether solvent having a boiling point of 120 to 250 ° C. at 750 mmHg, and the amount thereof is a photocurable composition. It is preferable to use in the range of 1% by mass to 90% by mass based on the total amount of the product.

  Specific examples of the ether solvent include propylene glycol methyl ether (121 ° C), dipropylene glycol monomethyl ether (190 ° C), tripropylene glycol monoethyl ether (242 ° C), dipropylene glycol dimethyl ether (175 ° C), propylene glycol. n-propyl ether (150 ° C.), dipropylene glycol n-propyl ether (212 ° C.), propylene glycol n-butyl ether (170 ° C.), dipropylene glycol n-butyl ether (229 ° C.), propylene glycol phenyl ether (243 ° C.) , Ethylene glycol monomethyl ether (138 ° C.), diethylene glycol monoethyl ether (202 ° C.), ethylene glycol monobutyl ether (171 ° C.), die Glycol monobutyl ether (202 ° C.) and the like.

  Furthermore, in this invention, you may use another organic solvent in combination with the said ether solvent from a viscosity adjustment and a soluble viewpoint. Specific examples of the solvent that can be used in the present invention include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether. Diethylene glycol monoethyl ether such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetylated products of diethylene glycol monoalkyl ethers such as diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. Examples include acetylated products of propylene glycol monoalkyl ether, lactones such as β-lactone, γ-lactone, and δ-lactone.

  In the above, the main component which comprises the photocurable composition by this invention was demonstrated. However, the photocurable composition according to the present invention is not limited to the above-described components, and may further include various additives well known in the art, if necessary, assuming use on a base material. . Although it does not specifically limit, It is preferable that the photocurable composition by this invention contains at least 1 sort (s) selected from the group which consists of surfactant, a coupling agent, and a reaction control agent as an additional component. Hereinafter, these components will be described.

(Surfactant)
By adding a surfactant to the photocurable composition of the present invention, when the above composition is applied on a substrate to form a photocured product, such as uneven drying, remaining coating, and uneven stripes Defects can be reduced or improved. The surfactant to be used is not particularly limited as long as the surface tension of the photocurable composition can be adjusted. In the present invention, for example, one kind of compound known as a fluorine-based surfactant and a silicone-based surfactant is used, or several compounds can be used in combination as required.

  Examples of silicone surfactants include dimethylpolysiloxane-polyoxyalkylene copolymers. As addition amount, when the total amount of a photocurable composition is 100 mass%, 0.001-5 mass% is preferable and 0.005-4 mass% is especially preferable. The effect by addition can be easily acquired by making the addition amount 0.001 mass% or more. On the other hand, when the addition amount is 5% by mass or less, it is possible to prevent problems such as repelling and shrinkage when applying the composition. Furthermore, when other materials are laminated after curing the photocurable composition, it is possible to prevent problems such as a decrease in adhesion and repelling.

(Coupling agent)
By adding a coupling agent to the photocurable composition of the present invention, the adhesion of the coating film obtained from the composition to the substrate can be improved. Since the component (C2) is also used as a coupling agent, the coupling agent here is other than the component (C2). As this coupling agent, various compounds well known in the art may be used, and it is preferable to appropriately select a compound effective for improving the adhesiveness according to the constituent material of the substrate.

Although not particularly limited, examples of the coupling agent that can be used in the present invention include 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl). Amino-based silane coupling agents such as aminopropylmethyldimethoxysilane and 3-aminopropyltrimethoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Glycidyl silane coupling agent such as ethyltrimethoxysilane,
Vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and allyltrimethoxysilane;
Examples include mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

  When using a coupling agent, the addition amount is preferably 0.1 to 20% by mass based on the mass of all solid components in the photocurable composition. From the viewpoint of sufficiently exhibiting the effect of improving adhesion, when the mass of all solid components of the photocurable composition is 100% by mass, the addition amount is preferably 0.1% by mass or more. On the other hand, from the viewpoint of maintaining the storage stability of the photocurable composition, the addition amount is preferably less than 20% by mass. Therefore, as one embodiment of the present invention, the addition amount of the coupling agent is preferably 0.1 to 20% by mass, and 0.5 to 15% by mass when the total amount of the photocurable composition is 100% by mass. Is particularly preferred. By appropriately adjusting the addition amount, the adhesion to the substrate can be effectively improved without adversely affecting other properties.

(Reaction control agent)
By adding a reaction control agent to the photocurable composition of the present invention, a stable composition can be obtained by controlling the reaction before light irradiation. The compound used as a reaction control agent in the present invention is not particularly limited, and may be a compound well known in the art. For example, in order to suppress the dark reaction, a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, or t-butylcatechol can be used. The addition amount of the reaction control agent is preferably 0.01 to 10% by mass based on the mass of all solid components in the photocurable composition.

  The photocurable composition according to the present invention can be prepared by uniformly mixing and dispersing the above-described various components using various mixing apparatuses. For mixing and dispersing, techniques well known in the art can be applied.

<Formation of cured coating film>
The photocurable composition according to the present invention can be formed on a substrate, dried, and a cured coating film can be easily formed by irradiating the coated surface with actinic rays. As one Embodiment of this invention, it is preferable that the said photocurable composition is formed as a thin film (cured material layer) patterned on the base material. The patterned cured product layer includes a lamination step of forming a photocurable composition layer on a substrate, and an exposure step of irradiating a predetermined portion of the layer with active light to form an exposed portion and a non-exposed portion. And a developing step of selectively removing the non-exposed portion in the layer.

  Here, the “base material” described in the present invention is not limited by the material constituting the base material, and may be any member that supports the thin film independently. For example, the base material is a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass; a sheet, film or substrate made of a synthetic resin such as polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin; aluminum plate, A metal substrate such as a copper plate, a nickel plate, or a stainless plate; a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member composed of various materials such as a glass substrate (color filter for LCD) having a color material layer on its surface; Good.

  In the laminating step, as one embodiment of the present invention, a photosensitive element including a support and a layer formed using the photocurable composition of the present invention formed on the support is formed. can do. As the support, it is preferable to use a film such as a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. The photocurable composition layer is formed by coating the photocurable composition on a support using a knife coater coating, a gravure coater coating, a roll coater coating, a spray coater coating or the like. It can be carried out by drying at a temperature of ~ 200 ° C, preferably 50-130 ° C for 1 second to 30 minutes. Such a drying treatment may be carried out using an apparatus such as a hot plate or a clean dryer in order to efficiently remove excess organic solvent from the photocurable composition layer. In consideration of the flatness and drying properties of the coating film, vacuum drying may be performed before heat drying. The thickness of the photocurable composition layer is preferably 0.1 to 300 μm, more preferably 0.2 to 30 μm, and still more preferably 0.2 to 10 μm.

  Moreover, in the said exposure process, the actinic ray to irradiate should just be optical energy which can harden a composition, and a technique well-known in this technical field is applicable. Although not particularly limited, for example, a carbon arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, or a visible light laser can be used as the light source. When irradiating the active light source, an exposed portion and a non-exposed portion can be formed by partially concealing the photocurable composition layer using a mask member or the like. In the laminating step, when the laminate is configured as a photosensitive element, it may be exposed from the support surface or may be exposed after the laminate is disposed at a predetermined location and the support is peeled off.

  Further, in the development step, after the exposure step, an unexposed portion in the layer is sprayed on the photocurable composition layer of the laminate by spraying an alkaline aqueous solution or immersing the laminate in the alkaline aqueous solution. Can be removed to obtain a patterned cured product layer. Examples of the alkaline aqueous solution include an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium metasilicate, or monoethanolamine, diethanolamine, triethanolamine, tetra An aqueous solution containing an organic base such as methylammonium hydroxide, triethylamine, n-butylamine or a salt thereof can be used. When the laminate is configured as a photosensitive element and exposed from the support side, development is performed after the support is peeled off.

After completion of the development process, the film is post-exposed with a light amount of 0.5 to 5 J / cm 2 using a light source such as a high-pressure mercury lamp, or post-heated at a temperature of 60 to 260 ° C. for 10 seconds to 120 minutes. It is preferable to carry out the post-curing step of the laminate by the method. By performing such a post-curing step, the hardness and adhesion of the patterned cured product layer can be further strengthened.

<Various devices>
The cured coating film formed using the photocurable composition of the present invention has low hygroscopicity and high hardness, and is excellent in adhesion to the substrate. Furthermore, since the said cured coating film has a high transmittance | permeability, it is suitable as a transparent member desired in field | areas, such as various display apparatuses. Although it does not specifically limit, the said cured coating film can be used conveniently as a transparent member for touchscreens, a transparent member for liquid crystal displays, a transparent member for organic TFTs, etc., for example. In addition, although the said various transparent member is a film-like single layer or multilayer member mainly comprised from the said cured coating film, support films or protections, such as PET film, PE film, PP film, as needed Even if it is combined with another film that functions as a film, or combined with two or more types of cured coatings, or it has been subjected to various surface treatments such as applying a release material to the surface. There may be. Usually, the said cured coating film itself can be used as a transparent member.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a touch panel configured using a cured coating film according to the present invention. As shown in FIG. 1, the touch panel includes a first transparent electrode 20 such as ITO provided on a base material 10 such as a glass substrate, a first insulating film 30 made of a cured coating film according to the present invention, and a first electrode. Two insulating films 32, and a second transparent electrode 24 disposed on the first insulating film 30 and conducting with the first transparent electrode 20 through the contact hole 22. In the touch panel having such a structure, it is preferable that the adhesion between each layer is good. Moreover, it is preferable that the contact hole for electrically connecting the first transparent electrode and the second transparent electrode is formed with high accuracy. The coating film obtained by curing the photocurable composition according to the present invention can be developed with an aqueous alkaline solution, and the coating film has low hygroscopicity and high hardness, and also has excellent adhesion to a substrate. It can be preferably used as a transparent material constituting the first and second insulating films. Thus, since the cured coating film by this invention is excellent in the said various characteristics desired, it becomes possible to implement | achieve a highly reliable touch panel by using them. Further, the cured coating film according to the present invention is not limited to the use of the interlayer insulating film of the touch panel, but can be suitably used as a transparent member desired in the field of other display devices or TFTs, and is required for various uses. High quality and reliability can be realized.

  Hereinafter, the contents of the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples, and it is obvious that a wide variety of embodiments can be configured without departing from the gist thereof.

1. Production of photocurable composition (production of alkali-soluble resin)
According to the following procedure, the alkali-soluble resin which is a (meth) acrylate copolymer containing a carboxyl group and an ethylenically unsaturated group was prepared.
(A) In a 1 L-scale four-necked flask, 264 g of propylene glycol monomethyl ether acetate and 66 g of methyl lactate were weighed, and the liquid temperature was kept at 90 ° C. while bubbling with nitrogen. The solution thus obtained is designated as solution (A).

(B) In a 1 L beaker, 240 g of propylene glycol monomethyl ether acetate, 60 g of methyl lactate, methacryloyloxytricyclo [5.2.1.0 2,6 ] decane (manufactured by Hitachi Chemical Co., Ltd., FANCYL FA-513M) 86. 4 g, 36.5 g of N-cyclohexylmaleimide, 106.7 g of 2-hydroxyethyl methacrylate, and 40.5 g of methacrylic acid were mixed and dissolved while bubbling with nitrogen. After confirming dissolution of N-cyclohexylmaleimide, 3 g of 2,2′-azobisisobutyronitrile was dissolved. The solution thus obtained is designated as solution (B).

  (C) Next, the solution (B) was continuously added dropwise to the solution (A) over 3 hours to provide a reaction solution, and then the reaction solution was maintained at 90 ° C. for 3 hours. While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of diethylene glycol dimethyl ether was added in several portions, In order to reduce, it added to the said reaction solution. As described above, after the reaction was performed at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., maintained at 120 ° C. for 1 hour, and then naturally cooled to give a monomer having a (meth) acryloyl group. Was obtained as a monomer unit. The solution thus obtained is designated as solution (C).

  (D) In order to introduce an ethylenically unsaturated bond (methacryloyl group) into the polymer, 2-methacryloyloxyethyl isocyanate and a tin-based catalyst are added to the solution (C) containing the polymer. The solution of (meth) acrylic copolymer having an ethylenically unsaturated bond at the side chain and / or terminal was obtained by holding at 80 ° C. for 2 to 3 hours and further naturally cooling. Hereinafter, the (meth) acrylic copolymer is abbreviated as resin A. 2-Methacryloyloxyethyl isocyanate was added in an amount of 0.5 mmol / g based on the mass of the polymer.

Example 1
Each component shown below was mix | blended and the photocurable composition was prepared. Specifically, first, the components (A), (B), (C), (F), (G) and (H) are placed in a 2 L disposable cup and cooled with cooling water for 30 minutes while homomixer. The above ingredients were mixed at 10,000 rpm to obtain a dispersion. Next, components (D) and (E) were added to the dispersion and dissolved while stirring to obtain a photocurable composition.
(A) Resin A 38.4 parts by mass (B) Silica fine particles (average particle diameter of about 10 nm, the same as those used in the following examples)
48.0 parts by mass (C) (C1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 38.4 parts by mass (C2) γ-acryloxypropyldimethylmethoxysilane 16.0 parts by mass (C3) EO-modified bisphenol A diacrylate 32.0 parts by mass (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 6.3 parts by mass (E) 1 , 2: 8,9 diepoxy limonene 10.5 parts by mass (F) propylene glycol monomethyl ether 160.0 parts by mass (other additives)
(G) SH-29PA (surfactant) (manufactured by Toray Dow Corning) 1.2 parts by mass (H) propylene glycol monomethyl ether acetate (organic solvent)
649.2 parts by mass

(Example 2)
In accordance with the same procedure as in Example 1, the following components were blended to prepare a photocurable composition.
(A) Resin A 38.4 parts by mass (B) Silica fine particles 48.0 parts by mass (C) (C1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 38.4 parts by mass ( C2) γ-acryloxypropyldimethylmethoxysilane 16.0 parts by mass (C3) 32.0 parts by mass of polyethylene glycol # 200 diacrylate (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Linopropan-1-one 6.3 parts by mass (E) 1,2: 8,9 diepoxy limonene 10.5 parts by mass (F) propylene glycol monomethyl ether 160.0 parts by mass (other additives)
(G) SH-29PA (surfactant) (manufactured by Toray Dow Corning) 1.2 parts by mass (H) propylene glycol monomethyl ether acetate (organic solvent)
649.2 parts by mass

(Example 3)
In accordance with the same procedure as in Example 1, the following components were blended to prepare a photocurable composition.
(A) Resin A 38.4 parts by mass (B) Silica fine particles 48.0 parts by mass (C) (C1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 38.4 parts by mass ( C2) γ-acryloxypropyldimethylmethoxysilane 16.0 parts by mass (C3) 1,4-butanediol diacrylate 32.0 parts by mass (D) 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one 6.3 parts by mass (E) 1,2: 8,9 diepoxy limonene 10.5 parts by mass (F) 160.0 parts by mass of propylene glycol monomethyl ether (other additives)
(G) SH-29PA (surfactant) (manufactured by Toray Dow Corning) 1.2 parts by mass (H) propylene glycol monomethyl ether acetate (organic solvent)
649.2 parts by mass

(Comparative Example 1)
In accordance with the same procedure as in Example 1, the following components were blended to prepare a photocurable composition.
(A) Resin A 62.4 parts by mass (C) (C1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 62.4 parts by mass (C2) γ-acryloxypropyldimethylmethoxysilane 16.0 parts by mass (C3) EO-modified bisphenol A diacrylate 32.0 parts by mass (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 6.3 parts by mass Parts (E) 1,2: 8,9 diepoxy limonene 10.5 parts by mass (F) propylene glycol monomethyl ether 160.0 parts by mass (other additives)
(G) SH-29PA (surfactant) (manufactured by Toray Dow Corning) 1.2 parts by mass (H) propylene glycol monomethyl ether acetate (organic solvent)
649.2 parts by mass

(Comparative Example 2)
In accordance with the same procedure as in Example 1, the following components were blended to prepare a photocurable composition.
(A) Resin A 43.7 parts by mass (B) Silica fine particles (average particle size 10 to 20 nm) 48.0 parts by mass (C) (C2) γ-acryloxypropyldimethylmethoxysilane 16.0 parts by mass (C3) EO-modified bisphenol A diacrylate 70.4 parts by mass (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 6.3 parts by mass (E) 1,2: 8,9 diepoxy limonene 10.5 parts by mass (F) propylene glycol monomethyl ether 160.0 parts by mass (other additives)
(G) SH-29PA (surfactant) (manufactured by Toray Dow Corning) 1.2 parts by mass (H) propylene glycol monomethyl ether acetate (organic solvent)
649.2 parts by mass

(Comparative Example 3)
In accordance with the same procedure as in Example 1, the following components were blended to prepare a photocurable composition.
(A) Resin A 38.4 parts by mass (B) Silica fine particles 48.0 parts by mass (C) (C1) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene 38.4 parts by mass ( C3) EO-modified bisphenol A diacrylate 48.0 parts by mass (D) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 6.3 parts by mass (E) 1, 2: 8,9 diepoxy limonene 10.5 parts by mass (F) propylene glycol monomethyl ether 160.0 parts by mass (other additives)
(G) SH-29PA (surfactant) (manufactured by Toray Dow Corning) 1.2 parts by mass (H) propylene glycol monomethyl ether acetate (organic solvent)
649.2 parts by mass

2. Evaluation of coating film Using each of the photocurable compositions prepared in each Example and each Comparative Example, a film is formed to a film thickness of 1 μm according to the following procedures (1) to (5). A sample was formed.
(1) Coating process: Each photocurable composition was coated on a glass substrate (AN100) using a spin coater.
(2) Temporary drying step: The substrate obtained in (1) above was allowed to stand on a hot plate heated to 90 ° C. for 3 minutes to remove excess organic solvent.
(3) Exposure process: A mask in which a 50 μm square transmission part and a 50 μm square light-shielding part were formed on quartz was used as a mask for pattern formation. As the actinic ray, UV light of about 200 mJ / cm 2 was irradiated with an exposure machine using an ultrahigh pressure mercury lamp to cure the 50 μm transmission part.
(4) Development step: An aqueous solution of Na 2 CO 3 having a concentration of about 0.05% was used as a developer, and developed in a shower type developing tank at a shower pressure of 0.025 kgf / cm 2 and a development temperature of 25 ° C. for about 30 seconds. After the development, in order to completely remove the Na 2 CO 3 aqueous solution, it was washed with pure water and dried by blowing air.
(5) Main baking process: It left still for about 40 minutes in 230 degreeC clean oven. Thereafter, it was taken out and allowed to cool to room temperature.

  Next, various characteristics of each sample obtained as described above were evaluated according to the following evaluation methods. The evaluation results are shown in Tables 1 and 2.

(A) Development characteristics It was visually determined whether development was possible within a development time of 30 seconds. If development is possible, “◯” is indicated. If development is not possible, “X” is indicated.

(B) Pencil hardness measurement The test was conducted in accordance with the pencil hardness test of JIS standard 5600.

(C) Martens hardness value measurement A Fischer scope HM-500 (manufactured by Fischer Instruments) was used, and measurement was performed under the conditions of a Vickers indenter, a load load of 35 mN, a load time of 20 seconds, and a measurement temperature of 25 ± 2 ° C.

(D) Hygroscopicity / Adhesion Evaluation The sample was allowed to stand in a pressure cooker (temperature 120 ° C., pressure 1 atm, humidity 100%) for 3 hours. Thereafter, when the sample was cooled to room temperature, a test based on a cross-cut tape peeling test of JIS standard 5600 was performed.

(E) Transmittance As the transmittance after the coating film was formed, the transmittance of the sample was measured at a measurement wavelength of 400 nm using UV-2400PC manufactured by Shimadzu Corporation.

(F) Heat resistance As the heat resistance after the coating film was formed, the sample was subjected to heat treatment at 250 ° C for 1 hour, and then the transmittance was measured. The measurement conditions are the same as (e).

DESCRIPTION OF SYMBOLS 10 Base material 20 1st transparent electrode 22 Contact hole 24 2nd transparent electrode 30 1st insulating layer 32 2nd insulating layer

Claims (10)

  1. (A) an alkali-soluble resin which is a (meth) acrylate copolymer having a carboxyl group and an ethylenically unsaturated group in the molecule;
    (B) silica fine particles;
    (C) a reactive monomer having one or more (meth) acryloyl groups in a single molecule,
    (C1) a reactive monomer containing a (meth) acrylate compound having a fluorene skeleton, and (C2) a (meth) acrylate compound having an alkoxysilane moiety;
    (D) A photocurable composition comprising a photopolymerization initiator.
  2.   (E) The photocurable composition of Claim 1 which further contains a polyfunctional epoxy compound as a component.
  3.   (F) The photocurable composition of Claim 1 or 2 which further contains an organic solvent as a component.
  4. The component (C1) is a di (meth) acrylate compound represented by the following general formula (1), and the component (C2) is a mono (meth) acrylate compound represented by the following general formula (2). The photocurable composition according to claim 1, 2 or 3.

    [Wherein, two R 1 s each independently represent a hydrogen atom or a methyl group, and two R 2 s each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, Each R 3 independently represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and m is an integer of 0 to 10].

    [Wherein R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrocarbon group having 1 to 10 carbon atoms, R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents It is an integer of 1-6, r is an integer of 0-2]
  5. The photocurable composition according to claim 1, 2, 3, or 4, wherein the (E) polyfunctional epoxy compound is a compound represented by the following general formula (3).

    [Wherein, R 7 , R 8 and R 9 each independently represent a hydrogen atom or a methyl group, but all of R 7 , R 8 and R 9 are not simultaneously hydrogen atoms]
  6.   6. The photocurable composition according to claim 3, 4 or 5, wherein the organic solvent (F) is an ether solvent having a boiling point of 120 to 250 ° C. at 750 mmHg.
  7.   The cured coating film obtained by irradiating an actinic ray to the photocurable composition in any one of Claims 1-6.
  8.   A transparent member for a touch panel having the cured coating film according to claim 7.
  9.   The transparent member for liquid crystal displays which has a cured coating film of Claim 7.
  10.   The transparent member for organic thin-film transistors which has the cured coating film of Claim 7.
JP2009184710A 2009-08-07 2009-08-07 Alkali-soluble photocurable composition, cured coating film using the composition and transparent member Pending JP2011039165A (en)

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