CN111433243B - Curable resin composition, laminate, optical filter, and compound - Google Patents
Curable resin composition, laminate, optical filter, and compound Download PDFInfo
- Publication number
- CN111433243B CN111433243B CN201880078115.9A CN201880078115A CN111433243B CN 111433243 B CN111433243 B CN 111433243B CN 201880078115 A CN201880078115 A CN 201880078115A CN 111433243 B CN111433243 B CN 111433243B
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- hydrocarbon group
- group
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
-
- 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
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Abstract
An embodiment of the present invention relates to a curable resin composition containing a polymerization initiator (D) and at least one compound (a) selected from the group consisting of compounds represented by the following formula (A1) and the following formula (A2), a laminate, and an optical filter. [ R ] 1 ～R 6 Each independently is a hydrogen atom or a methyl group, X 3 ～X 10 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 1 ～Y 4 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, m represents an integer of 0 to 20, and n represents an integer of 0 to 20.]
Description
Technical Field
An embodiment of the present invention relates to a curable resin composition, a laminate, an optical filter, and a compound.
Background
In recent years, in order to prevent scratches on a film or to improve adhesion between a substrate and an upper layer provided thereon, a laminate having a resin layer provided on a surface of a substrate by applying a curable resin composition has been widely used. Such a laminate is used as a display device such as a touch panel; surface materials for membrane switches (membrane switches), keypads (key pads), etc.; an electrode substrate of a liquid crystal cell (cell) constituting a liquid crystal display element; a retardation film, a film with a transparent electrode for a touch panel, a film for a near infrared cut filter (cut filter), and other optical films.
The laminate is required to have excellent properties such as scratch resistance, adhesion to a substrate or an upper layer, and hardness of the resin layer (for example, patent document 1 and patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6041372
Patent document 2: japanese patent laid-open No. 2017-47683
Disclosure of Invention
Problems to be solved by the invention
In recent years, development of a laminate having a base material, a resin layer, and an inorganic film formed thereon has been advanced, and a laminate material for obtaining the laminate has been studied. As one of reliability evaluations, a laminate used for an optical member and the like is required to have high adhesion at each layer interface after long-term retention under a high-temperature and high-humidity environment, but there is still room for further improvement in order to satisfy the above requirements with respect to a resin layer obtained from a conventional composition. Further, if the surface hardness of the resin layer is low, the occurrence of flaws that cause defects is caused, and therefore, it is desirable that the resin layer has a high hardness, but the higher the hardness, the lower the adhesion, and it is difficult to achieve both the hardness and the adhesion.
An embodiment of the present invention provides a curable resin composition capable of forming a resin layer having high surface hardness and excellent adhesion, particularly to an inorganic film.
Technical means for solving the problems
The present inventors have made intensive studies to solve the above-described problems, and as a result, have found that the above-described problems can be solved according to the following configuration examples, and have completed the present invention.
The constitution of the present invention is as follows, for example.
[1] A curable resin composition comprising a compound (A) selected from at least one of compounds represented by the following formulas (A1) and (A2) and a polymerization initiator (D):
[ chemical 1]
In the formula (A1), R 1 R is R 2 Each independently is a hydrogen atom or a methyl group, X 3 ～X 5 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 1 Y and Y 2 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and when m is 2 or more, a plurality of X' s 4 Y and Y 1 Can be the same or different;
[ chemical 2]
In the formula (A2), R 3 ～R 6 Each independently is a hydrogen atom or a methyl group, X 6 ～X 10 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 3 Y and Y 4 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and when n is 2 or more, a plurality of X' s 7 、X 10 、Y 4 R is R 6 May be the same or different.
[2]According to [1]]The curable resin composition, wherein X is 3 ～X 5 In (a) and (b)At least one and said X 6 ～X 10 At least one of them is independently a hydrocarbon group having 10 to 20 carbon atoms and having an adamantane ring.
[3]According to [1]]Or [2 ]]The curable resin composition, wherein Y 1 ～Y 2 At least one of and said Y 3 ～Y 4 At least one of them is independently a group represented by any one of the following (y 1) to (y 5):
[ chemical 3]
In the formulae (y 1) to (y 4), two are each a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2), and one is a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2) and the other is a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2).
[4] The curable resin composition according to any one of [1] to [3], which contains a compound (B) represented by the following formula (B):
[ chemical 4]
In the formula (B), R 10 Is a hydrogen atom or a methyl group, and L is an organic group having an alicyclic hydrocarbon group having 6 to 20 carbon atoms.
[5] The curable resin composition according to [4], wherein the content ratio of the compound (A) to the compound (B) (mass of the compound (A): mass of the compound (B)) in the curable resin composition is 1:99 to 99:1.
[6] The curable resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is 500 to 5000.
[7] The curable resin composition according to [4] or [5], wherein the molecular weight of the compound (B) is 180 to 600.
[8] A laminate comprising a base material and a resin layer formed of the curable resin composition according to any one of [1] to [7 ].
[9] The laminate according to [8], wherein at least one of the base material and the resin layer contains a pigment.
[10] An optical filter comprising the laminate according to [8] or [9] and a dielectric multilayer film.
[11] A compound represented by the following formula (a):
[ chemical 5]
In the formula (a), Y ' is an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, X ' is independently a hydrocarbon group having 6 to 20 carbon atoms and having an alicyclic hydrocarbon group, R ' is independently a hydrogen atom or a methyl group, p is 2 or 3, and a plurality of X ' and R ' may be the same or different.
[12] The compound of [11], wherein at least one of the X's is adamantanediyl.
[13] The compound according to [11] or [12], wherein the Y' is a group represented by any one of the following (Y1) to (Y5):
[ chemical 6]
In the formulae (y 1) to (y 4), two are each a bonding position to N constituting a urethane bond in the formula (a), and one is a bonding position to N constituting an isocyanuric ring in the formula (y 5), and the other is a bonding position to N constituting a urethane bond in the formula (a).
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, a curable resin composition capable of forming a resin layer having high surface hardness, excellent adhesion, particularly adhesion to an inorganic film, and a low haze value can be provided. Further, according to an embodiment of the present invention, a laminate and an optical filter having excellent wet heat resistance and few defects can be provided.
Detailed Description
Curable resin composition, compound
The curable resin composition (hereinafter, also referred to as "the present composition") according to one embodiment of the present invention contains at least one compound (a) selected from the compounds represented by the formula (A1) and the formula (A2) and a polymerization initiator (D).
The compound according to an embodiment of the present invention (hereinafter, also referred to as "compound (a)") is represented by the formula (a).
Since the present composition contains the compound (a) and the compound (a) is used, a resin layer having high surface hardness, a small haze value, and excellent adhesion to a substrate and an inorganic film, particularly excellent adhesion to an inorganic film due to suppression of hygroscopicity and the like even in the case of hot and humid conditions, can be easily obtained.
Further, since the resin layer is easily recovered in elasticity and easily exhibits toughness, improvement of scratch resistance of a film to be formed, improvement of yield by suppressing micro cracks at the time of die stamping or the like, and the like can be expected, and further, an effect of improving adhesion to a substrate or an inorganic film due to interaction between a urethane bond and the inorganic film or stress relaxation can be recognized.
The conventional polyfunctional urethane compound tends to absorb moisture, and the adhesion to a substrate or an inorganic film is reduced when it is heated in humidity, and further, the polyfunctional compound is used to achieve high hardness, and curing shrinkage is easily caused, whereby the adhesion to a substrate or an inorganic film is reduced. On the other hand, by using the compounds (a) and (a) having a large amount of alicyclic structures, a resin layer having a high hardness and being hydrophobic and hardly causing hardening shrinkage can be formed, and adhesion to a substrate or an inorganic film at the time of hardening or at the time of heat and humidity and high hardness can be simultaneously achieved.
Further, since the compounds (a) and (a) having urethane bonds are easy to synthesize compared with the compounds having urethane bonds, the present invention relating to the compounds (a) and (a) can be said to have high practical applicability in material development.
The present composition and compound (a) can be preferably used for optical members, particularly optical filters, and further near infrared cut-off filters.
< Compound (A) >
The compound (a) is at least one compound selected from the group consisting of compounds represented by the following formula (A1) and the following formula (A2). The compound represented by the following formula (A1) is more preferable in terms of easy obtaining of a resin layer or the like which is more excellent in adhesion to a substrate and adhesion to an inorganic film in wet heat and has small curing shrinkage.
[ chemical 7]
[ in formula (A1), R 1 R is R 2 Each independently is a hydrogen atom or a methyl group, X 3 ～X 5 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 1 Y and Y 2 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and when m is 2 or more, a plurality of X' s 4 Y and Y 1 May be the same or different.]
[ chemical 8]
[ in formula (A2), R 3 ～R 6 Each independently is a hydrogen atom or a methyl group, X 6 ～X 10 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 3 Y and Y 4 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and when n is 2 or more, a plurality of X' s 7 、X 10 、Y 4 R is R 6 May be the same or different. ]
X 3 ～X 10 Each independently represents a hydrocarbon group having 6 to 20 carbon atoms and having an alicyclic hydrocarbon group, and preferably represents a group comprising an alicyclic hydrocarbon.
X 3 ～X 10 The number of carbons of the hydrocarbon group is 6 or more, preferably 8 or more, more preferably 10 or more, and 20 or less, preferably 17 or less, more preferably 12 or less.
As X 3 ～X 10 Examples of the alicyclic hydrocarbon group contained in (a) include: cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, cyclopropanediyl, cyclobutenediyl, cyclopentenediyl, cyclohexendiyl, cycloheptenediyl, cyclooctenediyl, bicyclo [2.2.1 ]]Heptanediyl, trimethylbicyclo [2.2.1]Heptanediyl, bicyclo [2.2.2]Octanediyl, adamantanediyl, bicyclo [2.2.1]Heptenediyl, bicyclo [2.2.2]Octenediyl, cyclohexanedimethyl, tricyclodecanedimethyl, pentacyclodecanedimethyl, and the like.
Among these, cyclohexanedimethyl and adamantanediyl are preferable, and adamantanediyl is particularly preferable in terms of easily obtaining a resin layer having high hardness even if the concentration of the crosslinking group is low, and easily obtaining a resin layer having a more excellent balance between high hardness and low hardening shrinkage. That is, X is preferable 3 ～X 5 At least one of and X 6 ～X 10 At least one of which is preferably X 3 ～X 10 Each independently represents a hydrocarbon group having 10 to 20 carbon atoms and having an adamantane ring, and adamantanediyl is particularly preferred.
Y 1 ～Y 4 The number of carbons in the organic group is 6 or more, preferably 8 or more, more preferably 10 or more, and 40 or less, preferably 30 or less, more preferably 20 or less.
As Y 1 ～Y 4 The alicyclic hydrocarbon group contained in (B) may be mentioned as X 3 ～X 10 The alicyclic hydrocarbon groups contained in (a) are the same groups as those listed above.
It is possible to easily obtain a film having more excellent adhesion to a substrate and an inorganic film, particularly an inorganic film even when it is wet or hotIn terms of a resin layer having more excellent adhesion, Y is preferable 1 ～Y 2 At least one of Y 3 ～Y 4 At least one of which is preferably Y 1 ～Y 4 Each independently represents a hydrocarbon group having 6 to 20 carbon atoms which is an alicyclic hydrocarbon group or an organic group having 15 to 40 carbon atoms which contains an alicyclic hydrocarbon group and an isocyanurate ring, more preferably a group containing a cyclohexane ring or a norbornane ring, and still more preferably a group represented by any one of the following (y 1) to (y 5).
[ chemical 9]
In the formulae (y 1) to (y 4), two are each a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2), and one is a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2) and the other is a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2).
-CH in formula (y 3) 2 The position of-is preferably-CH 2 Meta-or para-Cy (Cy is cyclohexane ring).
m is preferably 0 to 5, and more preferably 0 in view of easiness of synthesis of the compound (a), yield at the time of synthesis, and the like.
n is preferably 0 to 5, and more preferably 0 in view of easiness of synthesis of the compound (a), yield at the time of synthesis, and the like.
In particular, the compound (a) is preferably a compound represented by the following formula (a) in terms of easily obtaining a resin layer or the like having high surface hardness, a small haze value, and excellent adhesion to a substrate and an inorganic film.
[ chemical 10]
In the formula (a), Y' is an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, and examples thereof includeY 1 ～Y 4 The same groups, etc., and preferred groups are also the same.
X' is independently a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, and examples thereof include X 3 ～X 10 The same groups, etc., and preferred groups are also the same.
R' is independently a hydrogen atom or a methyl group, and p is 2 or 3.
The plurality of X 'and R' may be the same or different.
The molecular weight of the compound (a) is preferably 500 to 5000, more preferably 500 to 2000, from the viewpoint that a resin layer having high surface hardness, a small haze value, and more excellent adhesion to a substrate and an inorganic film can be easily obtained.
The method for synthesizing the compound (a) is not particularly limited, and may be synthesized by a conventionally known method, but a method of reacting a compound represented by the following formula (a 1) with a compound represented by the following formula (a 2) is preferable. In addition, in carrying out the reaction, a compound represented by the following formula (a 3) may be used.
[ chemical 11]
(in the formula (a 1), R and X 1 Respectively with the R 1 X is X 3 The meaning is the same. )
[ chemical 12]
(in the formula (a 2), Y is the same as the Y 1 The meanings are the same, q is 2 or 3. )
[ chemical 13]
(in the formula (a 3), X 2 With said X 3 The meaning is the same. )
The reaction is preferably carried out in the presence of a catalyst, a solvent, or the like conventionally used in the reaction of a hydroxyl group with an isocyanate group.
The reaction is preferably carried out under heating, and the reaction temperature is preferably 50 to 90 ℃.
The content of the compound (a) in the present composition is preferably 1 mass% or more, more preferably 10 mass% or more, particularly preferably 30 mass% or more, and preferably 90 mass% or less, more preferably 80 mass% or less, particularly preferably 70 mass% or less, in terms of easily obtaining a resin layer or the like having high surface hardness, a small haze value, and more excellent adhesion to a substrate and an inorganic film.
< polymerization initiator (D) >)
The present composition comprises a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound capable of polymerizing the compound (a), the compound (B) or the compound (C) described below, and the like.
The polymerization initiator (D) contained in the present composition may be one kind or two or more kinds.
As the polymerization initiator (D), a known photopolymerization initiator may be used, or a thermal polymerization initiator may be used in combination as needed.
Examples of the polymerization initiator (D) include photopolymerization initiators described in JP-A2008-276194 and JP-A2003-241372.
Examples of the polymerization initiator (D) include an alkylbenzene ketone (alkylphenone) compound, an acylphosphine oxide compound, a biimidazole compound, a triazine compound, an oxime ester compound, a benzoin compound, and a benzophenone compound.
Examples of the alkylbenzene ketone compound include: α -hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one; α -aminoalkylphenones such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, and 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone; dialkoxyacetophenones such as 2, 2-dimethoxy-1, 2-diphenylethan-1-one and 2, 2-diethoxyacetophenone.
Examples of the acylphosphine oxide compound include: 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide.
Examples of the biimidazole compound include: 2,2 '-bis (2, 4-dichlorophenyl) -4,5,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2-chlorophenyl) -4,5,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dimethylphenyl) -4,5,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2-methylphenyl) -4,5,4',5 '-tetraphenyl-1, 2' -biimidazole and 2,2 '-diphenyl-4, 5,4',5 '-tetraphenyl-1, 2' -biimidazole.
Examples of the triazine compound include: 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.
Examples of the oxime ester compound include: n-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine and N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxocyclopentanemethyl-oxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine.
Examples of the benzoin compound include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Examples of the benzophenone compound include: benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3',4 '-bis (diethylamino) benzophenone, 4' -tetra (t-butylperoxy carbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone.
Among these, in terms of easily obtaining a resin layer and the like that is more excellent in hardenability and transparency, an acylphosphine oxide compound and an alkyl phenone compound are preferable, and an alkyl phenone compound is more preferable.
The content of the polymerization initiator (D) in the present composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 15 parts by mass or less, and even more preferably 8 parts by mass or less, relative to 100 parts by mass of the total of the compound (a), the compound (B) and the compound (C) described below, in terms of easily obtaining a resin layer or the like having high surface hardness, a small haze value, and more excellent adhesion to a substrate and an inorganic film.
< Compound (B) >
The present composition may contain a compound (B) represented by the following formula (B) in addition to the above-mentioned compound (a) in order to easily obtain a resin layer or the like having more excellent adhesion to a substrate and an inorganic film.
The compound (B) contained in the composition may be one or two or more.
[ chemical 14]
In the formula (B), R 10 Is a hydrogen atom or a methyl group.
L is an organic group having an alicyclic hydrocarbon group having 6 to 20 carbon atoms, and may be a group in which a hydrogen atom of the alicyclic structure is substituted with a group other than a (meth) acryloyl group or an atom such as a hydroxyl group, a hydrocarbon group or a halogen atom.
Examples of the alicyclic hydrocarbon group in L include those described as X 3 The same groups as exemplified in the above.
The carbon number of the organic group in L is preferably 8 or more, more preferably 10 or more, and preferably 15 or less, more preferably 12 or less.
Examples of the alicyclic hydrocarbon group contained in L include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, bicyclo [2.2.1]Heptyl, bicyclo [2.2.2]Octyl, tricyclo [3.3.1.1 3，7 ]Decyl and bicyclo [2.2.1]Heptenyl and bicyclo [2.2.2]Octenyl groups, and the like. Of these, in terms of easily obtaining a resin layer and the like having a more excellent balance between high hardness and low hardening shrinkage, tricyclic [3.3.1.1 ] is particularly preferred 3，7 ]Decyl.
The compound (B) is not particularly limited, and examples thereof include: cyclohexyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanediyl di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, isobornyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3, 5-dihydroxy-1-adamantyl (meth) acrylate, 3-phenylcarbamoyl-1-adamantyl (meth) acrylate, and the like.
The molecular weight of the compound (B) is preferably 180 or more, more preferably 200 or more, and preferably 600 or less, more preferably 400 or less, in terms of easily obtaining a resin layer or the like having high surface hardness, a small haze value, and more excellent adhesion to a substrate and an inorganic film.
When the compound (B) is contained in the composition, the content of the compound (B) in the composition is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, in terms of easily obtaining a resin layer or the like having high surface hardness, a small haze value, and more excellent adhesion to a substrate and an inorganic film.
The content ratio of the compound (A) to the compound (B) (mass of the compound (A): mass of the compound (B)) in the present composition is preferably 1:99 to 99:1, more preferably 80:20 to 50:50, for the same reason as described above.
< other ingredients >
The present composition may contain other components known in the art other than the above-mentioned compounds (a) and (B) and the polymerization initiator (D).
Examples of the other components include: the polyfunctional (meth) acrylic monomer other than the compound (a) and the compound (B) (hereinafter, also referred to as "compound (C)"), the monofunctional (meth) acrylic monomer other than the compound (B), a solvent, an antioxidant, an ultraviolet absorber, a pigment, an antireflection agent, a hard coat agent, an antistatic agent, a metal complex compound, a leveling agent, an antifoaming agent, and a coupling agent.
These other components may be one kind or two or more kinds, respectively.
The compound (C) is not particularly limited, and examples thereof include: specific examples of the poly (meth) acrylate of a polyhydric alcohol having three or more members such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol include: trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. In addition, there may be mentioned: tricyclodecane dimethanol di (meth) acrylate, alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, di or tri (meth) acrylate containing isocyanurate skeleton, di (meth) acrylate having bisphenol A skeleton, and the like.
The content of the compound (C) in the present composition is preferably 5 mass% or more, more preferably 15 mass% or more, and preferably 50 mass% or less, more preferably 40 mass% or less, in terms of easily obtaining a resin layer or the like having high surface hardness, a small haze value, and more excellent adhesion to a substrate and an inorganic film.
The proportion of the compound (C) in the present composition is preferably 10 mass% or more, more preferably 20 mass% or more, and preferably 55 mass% or less, more preferably 45 mass% or less, based on 100 mass% of the total of the compounds (a) to (C), for the same reason as described above.
The coloring matter is not particularly limited, and may be an inorganic compound or an organic compound, but is preferably an organic compound.
The dye may be appropriately selected from conventionally known dyes according to the intended use of the present composition, but when the present composition is used in a near infrared cut filter, a near infrared absorbing dye is preferably used.
Examples of such near infrared absorbing pigments include: squarylium (squarylium) compound, phthalocyanine compound, cyanine compound, dithiol compound, diimmonium compound, porphyrin compound, and croconium (croconium) compound.
The maximum absorption wavelength of the near infrared ray absorption dye is preferably 600nm or more, more preferably 620nm or more, particularly preferably 650nm or more, and preferably 800nm or less, more preferably 760nm or less, particularly preferably 740nm or less. If the maximum absorption wavelength is within such a wavelength range, sufficient near infrared absorption characteristics and visible light transmittance can be achieved. As the near infrared ray absorbing dye satisfying such absorption characteristics, squarylium compounds, phthalocyanine compounds, cyanine compounds, and Ketone onium compounds are particularly preferable.
The content of the pigment in the present composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and preferably 20 mass% or less, more preferably 10 mass% or less, in terms of excellent visible light transmittance, absorption of light of a desired wavelength, and the like.
Laminate (laminated body)
The resin layer formed from the present composition may be used alone as a resin film or the like, but is preferably used in the form of a laminate with a substrate.
The base material and the resin layer contained in the laminate may be one layer or two or more layers, respectively. The resin layer may be present only on one side of the substrate or on both sides.
The thickness of the resin layer (one layer) may be appropriately selected depending on the intended use, but is preferably 0.1 μm or more, more preferably 0.5 μm or more, particularly preferably 0.7 μm or more, and preferably 20 μm or less, more preferably 10 μm or less, particularly preferably 5 μm or less.
The substrate is preferably a transparent plate-like body having an average transmittance of 85% or more of light in a wavelength region of 400nm to 700nm, and is preferably formed of a material that transmits visible light, and examples thereof include a resin substrate and a glass substrate. Among them, a resin base material is preferable because it is excellent in processability and adhesion to the resin layer is excellent.
Examples of the resin base material include: substrates such as polycarbonate-based resins, acrylic-based resins, polyester-based resins, polyether-based resins, polyolefin-based resins, epoxy-based resins, alkyd-based resins, melamine-based resins, polyurethane-based resins, polyimide-based resins, polyamide-based resins, and norbornene-based resins.
Examples of the glass substrate include a substrate such as soda-lime glass (soda-lime glass), borosilicate glass (borosilicate glass), alkali-free glass (alkali free glass), quartz glass, chemically strengthened glass, physically strengthened glass, copper-containing phosphate glass, and copper-containing fluorophosphate glass.
At least one of the base material and the resin layer preferably contains a pigment. In particular, when the laminate is used for a near infrared cut filter, a near infrared absorbing dye is preferably used.
The near infrared absorbing dye may be the same as the above dye, and the content of the dye in the base material or the resin layer may be the same as the content ratio of the dye in the present composition.
The thickness of these substrates may be appropriately selected depending on the intended use, and is preferably 10 μm or more, more preferably 20 μm or more, particularly preferably 25 μm or more, and is preferably 100mm or less, more preferably 50mm or less, particularly preferably 10mm or less.
The method for producing the laminate is not particularly limited, and the laminate may be formed by forming a resin layer (film) from the composition on a support, then peeling the support, and laminating the obtained resin layer (film) with a substrate, but it is preferable to apply the composition on the substrate and cure the composition.
As the method of the coating, a known method can be appropriately selected. For example, there may be mentioned: bar coating, dip coating, cast coating, spray coating, spin coating, bead coating, knife coating, roll coating, curtain coating, slit coater, gravure coater, slot reverse coater (slit reverse coater method), micro gravure, unfilled corner roller coater, screen printing, flexo printing.
After the present composition is applied to the substrate, the applied present composition may be dried, for example, before hardening as described below.
The method of hardening is not particularly limited, and there are a method of hardening by heating, a method of irradiating light, and the like, and particularly, a method of irradiating light is preferable.
The light to be irradiated is preferably light having a wavelength of 200nm to 500 nm. The hardening may be promoted by heating at the time of irradiation with light, after irradiation with light, or the like.
The temperature condition upon irradiation with light is preferably 0 ℃ or higher, more preferably 10 ℃ or higher, and preferably 100 ℃ or lower, more preferably 60 ℃ or lower.
The environment in which light is irradiated may be the atmosphere, but an inert gas environment is preferable in terms of reducing the influence of oxygen inhibition, and the like. The inert gas may be nitrogen, argon, or the like.
The light irradiation amount (cumulative light amount) can be, for example, 50mJ/cm 2 ～20000mJ/cm 2 The range is selected so that the nitrogen atmosphere is preferably 100mJ/cm 2 The above is more preferably 200mJ/cm 2 Above, and preferably 10000mJ/cm 2 Hereinafter, more preferably 8000mJ/cm 2 The following is given.
The laminate may further have an inorganic film. The inorganic film may be formed on the substrate, but is preferably formed on the resin layer in order to further exert the effect of providing the resin layer.
As the inorganic film, there may be mentioned: conductive films such as dielectric multilayer films and Indium Tin Oxide (ITO) films; metals such as gold, platinum, and copper, their oxides, and films of alloys containing these metals.
The laminate is preferably used for a display device such as a touch panel; surface materials for membrane switches, keypads, etc.; an electrode substrate of a liquid crystal cell constituting the liquid crystal display element; in particular, the film is preferably used for a near infrared cut filter (film) such as a retardation film, a film with a transparent electrode for a touch panel, and an optical film such as a film for a near infrared cut filter.
Optical Filter
The optical filter according to an embodiment of the present invention preferably has the laminate and the dielectric multilayer film. The dielectric multilayer film may be formed directly on the substrate, but is preferably formed on the resin layer in order to further exert the effect of providing the resin layer.
The optical filter is not particularly limited, but is preferably a near infrared cut filter.
The dielectric multilayer film is preferably a film having a near infrared ray reflecting ability. The dielectric multilayer film may be provided on one side or both sides of the laminate. When the optical filter is provided on one surface, an optical filter excellent in manufacturing cost and manufacturing easiness can be obtained, and when the optical filter is provided on both surfaces, an optical filter having high strength and less liable to warp can be obtained.
Examples of the dielectric multilayer film include a film in which high refractive index material layers and low refractive index material layers are alternately laminated.
As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more may be used, and a material having a refractive index in the range of usually 1.7 to 2.5 may be selected. Examples of such a material include materials containing titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc sulfide, indium oxide, or the like as a main component, and a small amount (for example, 0% to 10% relative to the main component) of titanium oxide, tin oxide, cerium oxide, or the like.
As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less may be used, and a material having a refractive index in the range of usually 1.2 to 1.6 may be selected. Examples of such a material include silicon dioxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.
The method of stacking the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are stacked is formed. For example, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately stacked may be formed directly on the laminate by a chemical vapor deposition (chemical vapor deposition, CVD) method, a sputtering method, a vacuum evaporation method, an ion-assisted evaporation method, an ion plating method, or the like.
In this case, the surface of the resin layer may be subjected to a surface treatment such as corona treatment or plasma treatment.
When the wavelength to be masked is λ (nm), the thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ. When the thicknesses of the high refractive index material layer and the low refractive index material layer are within the above-described range, the optical film thickness calculated by the product (n×d) of the refractive index (n) and the film thickness (d) becomes substantially the same value as λ/4, and the shielding and transmission of a specific wavelength tend to be easily controlled in terms of the relationship between the optical characteristics of reflection and refraction.
The value of λ (nm) is, for example, 700nm or more, preferably 750nm or more, and 1400nm or less, preferably 1300nm or less.
The total number of layers of the high refractive index material and the low refractive index material in the dielectric multilayer film is preferably 5 or more, more preferably 10 or more, and preferably 60 or less, more preferably 50 or less, based on the entire optical filter.
If warpage occurs in the optical filter when the dielectric multilayer film is formed, a method of forming the dielectric multilayer film on both sides of the laminate, or a method of irradiating electromagnetic waves such as ultraviolet rays on the surface of the laminate on which the dielectric multilayer film is formed may be performed in order to eliminate the warpage. In the case of irradiating electromagnetic waves, irradiation may be performed during formation of the dielectric multilayer film, or may be performed separately after formation.
In the optical filter, functional films such as an antireflection film, a hard coat film, and an antistatic film may be provided on a surface of the laminate opposite to the surface on which the dielectric multilayer film is provided or on a surface of the dielectric multilayer film opposite to the surface on which the laminate is provided, in order to improve the surface hardness of the substrate or the dielectric multilayer film, improve the chemical resistance, prevent static electricity, and eliminate damage, within a range that does not impair the effects of the present invention.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[ measurement of molecular weight ]
The molecular weight of the compound synthesized in the following synthesis example was measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) under the following measurement conditions using GPC columns (G2000 HXL 2, G3000HXL 1, G4000HXL 1) manufactured by eastern (Tosoh) (strand).
GPC measurement conditions:
dissolution solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Sample concentration: 1.0 mass%
Sample injection amount: 100 mu L
Column temperature: 40 DEG C
Detector: differential refractometer
Standard substance: monodisperse polystyrene
Synthesis example 1 Synthesis of Compound (A-1)
In a reaction vessel equipped with a stirring device, a thermometer and a condenser, 0.0194g of 2, 6-di-t-butyl-4-methylphenol, 27.047g (0.12 mol) of 3-hydroxy-1-adamantylacrylate (manufactured by Mitsubishi gas chemical (stock)), and 26.481g (0.12 mol) of isophorone diisocyanate (manufactured by Evonik, molecular weight: 222) were dissolved in 19g of methyl ethyl ketone (methyl ethyl ketone, MEK) at room temperature, 0.405g of dioctyltin dilaurate was added, and then the mixture was heated to 70℃with stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution was transparent, 27.047g of 3-hydroxy-1-adamantyl acrylate was added thereto, and the reaction was continued at 70 ℃. When the absorption spectrum of the isocyanate group was confirmed in the infrared absorption spectrum (2280 cm -1 ) After almost disappearance, the reaction was terminated.
The reaction mixture was purified by column chromatography on silica gel using ethyl acetate/hexane as a dissolution liquid, whereby the acrylic urethane compound (A-1) (molecular weight: 667) was obtained.
Hydrogen nuclear magnetic resonance of compound (A-1) using a nuclear magnetic resonance apparatus (trade name "JNM-ECX400", manufactured by Japan electronics (Co., ltd.)) 1 H-nuclear magnetic resonance， 1 H-NMR) spectrum was measured. As a result, it was confirmed that the structure of the obtained compound (A-1) was represented by the following formula (A-1).
1 H-NMR(DMSO-d 6 )；δ1.04(m，22H)，1.51(m，1H)，2.02(m，20H)，2.26(d，1H)，2.46(d，1H)，3.79(m，1H)，5.86(d，2H)，6.06(t，2H)，6.21(d，2H)，6.82(s，1H)，6.93(s，1H)
[ 15]
Synthesis example 2 Synthesis of Compound (A-2)
In a reaction vessel equipped with a stirrer and a thermometer and a condenser, 0.0194g of 2, 6-di-t-butyl-4-methylphenol, 27.047g (0.12 mol) of 3-hydroxy-1-adamantylacrylate (manufactured by Mitsubishi gas chemical (stock)), and 24.7g (0.12 mol) of norbornane diisocyanate (manufactured by Mitsubishi gas chemical (stock)) were dissolved in 19g of MEK at room temperature, 0.405g of dioctyltin dilaurate was added thereto, and then the temperature was raised to 70℃with stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution was transparent, 27.047g of 3-hydroxy-1-adamantyl acrylate was added thereto, and the reaction was continued at 70 ℃. When the absorption spectrum of the isocyanate group was confirmed in the infrared absorption spectrum (2280 cm -1 ) After almost disappearance, the reaction was terminated.
The reaction mixture was purified by column chromatography on silica gel using ethyl acetate/hexane as a dissolution liquid, whereby the acrylic urethane compound (A-2) (molecular weight: 651) was obtained.
Based on the results of Synthesis example 1 and the molecular weight, the structure of the obtained compound (A-2) was considered to be represented by the following formula (A-2).
[ 16]
Synthesis example 3 Synthesis of Compound (A-3)
In a reaction vessel equipped with a stirring device, a thermometer and a condenser, 0.0194g of 2, 6-di-t-butyl-4-methylphenol, 27.047g (0.12 mol) of 3-hydroxy-1-adamantylacrylate (manufactured by Mitsubishi gas chemical (stock)), and 23.3g (0.12 mol) of 1, 3-hydrogenated xylylene diisocyanate (manufactured by active material chemical (katsuzai chemical) (stock)) were dissolved in 19g of MEK at room temperature, 0.405g of dioctyltin dilaurate was added thereto, and then the temperature was raised to 70℃with stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution was transparent, 27.047g of 3-hydroxy-1-adamantyl acrylate was added thereto, and the reaction was continued at 70 ℃. When the absorption spectrum of the isocyanate group was confirmed in the infrared absorption spectrum (2280 cm -1 ) After almost disappearance, the reaction was terminated.
The reaction mixture was purified by column chromatography on silica gel using ethyl acetate/hexane as a dissolution liquid, whereby the acrylic urethane compound (A-3) (molecular weight: 639) was obtained.
Based on the results of Synthesis example 1 and the molecular weight, the structure of the obtained compound (A-3) was considered to be represented by the following formula (A-3).
[ chemical 17]
Synthesis example 4 Synthesis of Compound (A-4)
In a reaction vessel equipped with a stirrer and a thermometer and a condenser, 0.0194g of 2, 6-di-t-butyl-4-methylphenol, 27.047g (0.12 mol) of 3-hydroxy-1-adamantylacrylate (manufactured by Mitsubishi gas chemical (stock)), and 31.4g (0.12 mol) of 4,4' -methylenebis (cyclohexyl isocyanate) (manufactured by Evonik) were dissolved in 19g of MEK at room temperature, 0.405g of dioctyl tin dilaurate was added thereto, and the mixture was heated to 70℃with stirring. Upon confirmation of dissolution of the 3-hydroxy-1-adamantyl acrylateAfter the solution had been made transparent, 27.047g of 3-hydroxy-1-adamantylacrylate was added thereto, and the reaction was continued at 70 ℃. When the absorption spectrum of the isocyanate group was confirmed in the infrared absorption spectrum (2280 cm -1 ) After almost disappearance, the reaction was terminated.
The reaction mixture was purified by column chromatography on silica gel using ethyl acetate/hexane as a dissolution liquid, whereby the acrylic urethane compound (A-4) (molecular weight: 707) was obtained.
Based on the results of Synthesis example 1 and the molecular weight, the structure of the obtained compound (A-4) was considered to be represented by the following formula (A-4).
[ chemical 18]
Synthesis example 5 Synthesis of Compound (A-5)
In a reaction vessel equipped with a stirring device, a thermometer and a condenser, 0.0194g of 2, 6-di-t-butyl-4-methylphenol, 27.047g (0.12 mol) of 3-hydroxy-1-adamantylacrylate (manufactured by Mitsubishi gas chemical (stock)), and 26.481g (0.12 mol) of isophorone diisocyanate (manufactured by Evonik, molecular weight: 222) were dissolved in 19g of MEK at room temperature, 0.405g of dioctyltin dilaurate was added, and then the temperature was raised to 70℃with stirring. After confirming that 3-hydroxy-1-adamantyl acrylate was dissolved and the solution was transparent, 23.8g (0.12 mol) of 1, 4-cyclohexanedimethanol monoacrylate (produced by Japanese chemical Co., ltd., molecular weight: 198) was added thereto, and the reaction was continued at 70 ℃. When the absorption spectrum of the isocyanate group was confirmed in the infrared absorption spectrum (2280 cm -1 ) After almost disappearance, the reaction was terminated.
The reaction mixture was purified by column chromatography on silica gel using ethyl acetate/hexane as a dissolution liquid, whereby an acrylic urethane compound (A-5) (molecular weight: 643) was obtained.
Based on the results of Synthesis example 1 and the molecular weight, the structure of the obtained compound (A-5) was considered to be represented by the following formula (A-5).
[ chemical 19]
Synthesis example 6 Synthesis of Compound (A-6)
In a reaction vessel having a stirring device, a thermometer and a condenser, 0.0194g of 2, 6-di-T-butyl-4-methylphenol, 27.047g (0.12 mol) of 3-hydroxy-1-adamantylacrylate (manufactured by Mitsubishi gas chemical (stock)), and isocyanurate of isophorone diisocyanate (trade name: wei Sida na (VESTANAT) T1890/100, manufactured by Evonik) were dissolved in 29.0g of MEK 19 at room temperature, 0.405g of dioctyltin dilaurate was added thereto, and then the temperature was raised to 70℃with stirring. After confirming that the solution was uniformly transparent, 27.047g of 3-hydroxy-1-adamantylacrylate and 29.0g of isophorone diisocyanate were additionally added, and the reaction was continued at 70 ℃. When the absorption spectrum of the isocyanate group was confirmed in the infrared absorption spectrum (2280 cm -1 ) After almost disappearance, the reaction was terminated.
The reaction mixture was purified by column chromatography on silica gel using ethyl acetate/hexane as a dissolution liquid, whereby an acrylic urethane compound (A-6) (molecular weight: 1334) was obtained.
Compound (A-6) measured by the same apparatus as that described above 1 As a result of H-NMR measurement, it was confirmed that the structure of the obtained compound (A-6) was represented by the following formula (A-6).
1 H-NMR(DMSO-d 6 )；δ1.04-2.02(m，87H)，2.26(m，3H)，2.46(m，3H)，3.79(m，3H)，δ5.86(m，3H)，6.06(m，3H)，6.21(m，3H)，6.99(m，3H)
[ chemical 20]
EXAMPLE 1 preparation of solution of curable resin composition
A curable resin composition was prepared by adding 3.0g of compound (A-1) and 0.09g of compound (D-1) to a 20mL sample tube and diluting with 10g of MEK.
[ examples 2 to 11 and comparative examples 1 to 4] preparation of curable resin compositions
A composition was prepared in the same manner as in example 1, except that the compounds described in table 1 were used in the proportions described in table 1. The values in the columns of the compositions in table 1 are the proportions (parts by mass) of the compounds used when the total of the compounds (a) to (C) is 100 parts by mass.
Details of the compounds (B-1) to (B-4), the compounds (C-1) to (C-3) and the compounds (D-1) to (D-3) shown in Table 1 are shown in Table 2.
[ haze measurement ]
The curable resin compositions obtained in the examples and comparative examples were applied to a substrate (norbornane-based resin film [ JSR (strand) manufacture, atton) FEKE100, film thickness 100 μm ]) so that the thickness of the obtained resin layer became 3 μm, and cured by ultraviolet irradiation in a nitrogen atmosphere, to obtain a substrate with a resin layer. The haze value of the resin layer-equipped substrate thus obtained was measured by a method according to Japanese Industrial Standard (Japanese Industrial Standards, JIS) K7136 using a haze meter (manufactured by Toyo Seisakusho machine Co., ltd., trade name: hazjia-gard II). The haze value was determined to be 0.1 or less. The results are shown in Table 1.
[ Pencil hardness test ]
The hardness of the resin layer in the obtained resin layer-carrying substrate was measured by pencil hardness test in the same manner as in the haze measurement according to the method described in JIS K5600-5-4.
Specifically, after the humidity of the resin layer-attached substrate was adjusted at 25 ℃ and 60% rh for 2 hours, the surface of the resin layer was scratched with a 4.9N load using a test pencil, and the highest pencil hardness, which was not damaged, among the five test materials was set as an evaluation value. The pencil hardness was judged to be good when B or more. The results are shown in Table 1.
[ test of moist Heat resistance (adhesion) ]
In the same manner as in the haze measurement, a substrate with a resin layer was obtained. On the resin layer of the obtained resin layer-equipped substrate, the following inorganic film (dielectric multilayer film, ITO sputtering film or gold vapor plating film) was formed. The obtained substrate with inorganic film was placed in a constant temperature and humidity tank under 85 ℃ and 85% rh for 1000 hours. Thereafter, the adhesion between the inorganic film and the resin layer was evaluated as follows. The results are shown in Table 1.
Dielectric multilayer film: siO is alternately laminated by a conventionally known vapor deposition method 2 (film thickness: 10 nm-100 nm) layer and TiO 2 ( Film thickness: 10nm to 120 nm) layer film (lamination number 28, total thickness 3 μm )
ITO sputtered film: film (thickness: 500 nm) formed by vapor deposition of ITO by a conventionally known method
Gold vapor deposition film: film (thickness: 500 nm) obtained by vapor deposition of gold by a conventionally known method
The inorganic film was scored with 11 cuts extending from the vertical direction to the horizontal direction and reaching the resin layer at 1mm intervals in a checkered pattern using a cutter, and a total of 100 squares were scored. An adhesive tape (registered trademark) was attached to the scored surface, and the number of inorganic films remaining on the substrate was evaluated by peeling off the adhesive tape after the adhesive tape (trade name: CT 24) was manufactured by Nichiban (strand). The number of inorganic films remaining on the substrate side after the tape was peeled off from the 100 squares was 90 or more, and the adhesion was determined to be good.
TABLE 2
Claims (11)
1. A curable resin composition comprising a compound (A) selected from at least one of compounds represented by the following formulas (A1) and (A2) and a polymerization initiator (D):
in the formula (A1), R 1 R is R 2 Each independently is a hydrogen atom or a methyl group, X 3 ～X 5 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 1 Y and Y 2 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, m is an integer of 0 to 20, and when m is 2 or more, a plurality of X' s 4 Y and Y 1 Can be the same or different;
in the formula (A2), R 3 ～R 6 Each independently is a hydrogen atom or a methyl group, X 6 ～X 10 Each independently is a hydrocarbon group having 6 to 20 carbon atoms having an alicyclic hydrocarbon group, Y 3 Y and Y 4 Each independently represents an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, n is an integer of 0 to 20, and when n is 2 or more, a plurality of X' s 7 、X 10 、Y 4 R is R 6 Which may be the same or different,
the X is 3 ～X 5 At least one of and the X 6 ～X 10 At least one of them is independently a hydrocarbon group having 10 to 20 carbon atoms and having an adamantane ring.
2. Root of Chinese characterThe curable resin composition according to claim 1, wherein Y 1 ～Y 2 At least one of them is independently a group represented by any one of the following (Y1) to (Y4), and Y is 3 ～Y 4 Each independently is a group represented by the following (y 5):
in the formulae (y 1) to (y 4), two are each a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2), and one is a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2) and the other is a bonding position to N constituting a urethane bond in the formula (A1) or the formula (A2).
3. The curable resin composition according to claim 1 or 2, comprising a compound (B) represented by the following formula (B):
in the formula (B), R 10 Is a hydrogen atom or a methyl group, and L is an organic group having an alicyclic hydrocarbon group having 6 to 20 carbon atoms.
4. The curable resin composition according to claim 3, wherein the content ratio of the compound (a) to the compound (B) in the curable resin composition is the mass of the compound (a): the mass of the compound (B) is 1:99 to 99:1.
5. the curable resin composition according to claim 1 or 2, wherein the molecular weight of the compound (a) is 500 to 5000.
6. The curable resin composition according to claim 3, wherein the molecular weight of the compound (B) is 180 to 600.
7. A laminate comprising a base material and a resin layer formed from the curable resin composition according to any one of claims 1 to 6.
8. The laminate according to claim 7, wherein at least one of the base material and the resin layer contains a pigment.
9. An optical filter comprising the laminate according to claim 7 or 8 and a dielectric multilayer film.
10. A compound represented by the following formula (a):
in the formula (a), Y ' is an organic group having 6 to 40 carbon atoms and having an alicyclic hydrocarbon group, X ' is independently a hydrocarbon group having 6 to 20 carbon atoms and having an alicyclic hydrocarbon group, R ' is independently a hydrogen atom or a methyl group, p is 2 or 3, and a plurality of X ' and R ' may be the same or different,
at least one of the X's is adamantanediyl.
11. The compound according to claim 10, wherein Y "is a group represented by any one of the following (Y1) to (Y5):
in the formulae (y 1) to (y 4), two are each a bonding position to N constituting a urethane bond in the formula (a), and one is a bonding position to N constituting an isocyanuric ring in the formula (y 5), and the other is a bonding position to N constituting a urethane bond in the formula (a).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-242587 | 2017-12-19 | ||
| JP2017242587 | 2017-12-19 | ||
| PCT/JP2018/046280 WO2019124294A1 (en) | 2017-12-19 | 2018-12-17 | Curable resin composition, layered body, optical filter, and compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111433243A CN111433243A (en) | 2020-07-17 |
| CN111433243B true CN111433243B (en) | 2023-05-02 |
Family
ID=66994695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880078115.9A Active CN111433243B (en) | 2017-12-19 | 2018-12-17 | Curable resin composition, laminate, optical filter, and compound |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7192796B2 (en) |
| KR (1) | KR102577455B1 (en) |
| CN (1) | CN111433243B (en) |
| TW (1) | TWI781263B (en) |
| WO (1) | WO2019124294A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214114B (en) * | 2021-05-13 | 2023-03-31 | 珠海赛纳三维科技有限公司 | Active group blocked diisocyanate for 3D object printing, composition, and method and device for printing 3D object |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307844A (en) * | 1987-06-06 | 1988-12-15 | Hakusui Kagaku Kogyo Kk | Adamantyl diacrylate or dimethacrylate derivative and polymer comprising said derivative as polymer component |
| US6670499B1 (en) * | 1999-11-08 | 2003-12-30 | Daicel Chemical Industries, Ltd. | Adamantane derivatives and processes for the preparation thereof |
| TW200635977A (en) * | 2005-01-24 | 2006-10-16 | Idemitsu Kosan Co | Epoxy resin composition and optical material using same |
| CN103492446A (en) * | 2011-05-16 | 2014-01-01 | 三井化学株式会社 | Novel compound, composition containing said compound, and cured product |
| CN104166334A (en) * | 2013-05-17 | 2014-11-26 | 株式会社理光 | Cleaning blade, image forming apparatus, and process cartridge |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041372U (en) | 1983-08-26 | 1985-03-23 | ナショナル住宅産業株式会社 | Packing structure of wall panel group |
| JPH02223904A (en) * | 1989-02-27 | 1990-09-06 | Sumitomo Electric Ind Ltd | Coated optical fiber |
| JP2001131138A (en) * | 1999-11-08 | 2001-05-15 | Daicel Chem Ind Ltd | Adamantane derivative and method for producing the same |
| JP2015124227A (en) | 2013-12-25 | 2015-07-06 | 日本合成化学工業株式会社 | Active energy ray curable resin composition and coating agent composition |
| JP6757177B2 (en) * | 2015-05-21 | 2020-09-16 | 株式会社巴川製紙所 | Protective film, film laminate and polarizing plate |
| JP6740810B2 (en) | 2015-09-01 | 2020-08-19 | 東洋紡株式会社 | Hard coat polyester film |
| JP6848481B2 (en) | 2016-07-29 | 2021-03-24 | 三菱ケミカル株式会社 | (Meta) acryloyl isocyanate, (meth) acryloyl isocyanate-modified inorganic oxide fine particles and their manufacturing method |
-
2018
- 2018-12-17 CN CN201880078115.9A patent/CN111433243B/en active Active
- 2018-12-17 KR KR1020207017235A patent/KR102577455B1/en active IP Right Grant
- 2018-12-17 WO PCT/JP2018/046280 patent/WO2019124294A1/en active Application Filing
- 2018-12-17 JP JP2019561070A patent/JP7192796B2/en active Active
- 2018-12-18 TW TW107145686A patent/TWI781263B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307844A (en) * | 1987-06-06 | 1988-12-15 | Hakusui Kagaku Kogyo Kk | Adamantyl diacrylate or dimethacrylate derivative and polymer comprising said derivative as polymer component |
| US6670499B1 (en) * | 1999-11-08 | 2003-12-30 | Daicel Chemical Industries, Ltd. | Adamantane derivatives and processes for the preparation thereof |
| TW200635977A (en) * | 2005-01-24 | 2006-10-16 | Idemitsu Kosan Co | Epoxy resin composition and optical material using same |
| CN103492446A (en) * | 2011-05-16 | 2014-01-01 | 三井化学株式会社 | Novel compound, composition containing said compound, and cured product |
| CN104166334A (en) * | 2013-05-17 | 2014-11-26 | 株式会社理光 | Cleaning blade, image forming apparatus, and process cartridge |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI781263B (en) | 2022-10-21 |
| WO2019124294A1 (en) | 2019-06-27 |
| KR102577455B1 (en) | 2023-09-12 |
| JP7192796B2 (en) | 2022-12-20 |
| KR20200090821A (en) | 2020-07-29 |
| CN111433243A (en) | 2020-07-17 |
| JPWO2019124294A1 (en) | 2021-01-14 |
| TW201934591A (en) | 2019-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101994562B1 (en) | Resin film, laminated film, optical member, display member, front plate, and method for producing laminated film | |
| KR102066759B1 (en) | Hard coating composition and composition for forming high refractive index anti-blocking layer | |
| KR20170103644A (en) | Hard coating film | |
| EP2980165B1 (en) | Coating composition | |
| KR20020083487A (en) | Filter for plasma display panel | |
| JP2013204001A (en) | Active energy ray-curable resin composition and laminate using the same | |
| WO2020079992A1 (en) | Transfer film, hardened film production method, layered body production method, and touch panel production method | |
| CN111433243B (en) | Curable resin composition, laminate, optical filter, and compound | |
| JP2010134436A (en) | Filter for display | |
| JP5925011B2 (en) | Hard coating composition | |
| TW201809060A (en) | Resin composition, cured film, method for producing cured film, and display device | |
| US20160032109A1 (en) | Coating composition | |
| TW201247805A (en) | Composition used to form low refractive layer and anti-reflection film, polarizer and display device thereof | |
| KR102405075B1 (en) | Active energy ray-curable composition, cured product, and film | |
| KR20170040598A (en) | Hard coating composition and hard coating film formed therefrom | |
| EP4254022A1 (en) | Optical laminate and article | |
| JP5691334B2 (en) | Method for producing transparent conductive laminate | |
| KR101771288B1 (en) | Transparent resin laminate | |
| WO2017155003A1 (en) | Transfer film, electrode protective film, laminate, capacitive input device, method for manufacturing capacitive input device, and method for manufacturing transfer film | |
| KR102420383B1 (en) | Hard coating composition and hard coating film formed therefrom | |
| KR20170103646A (en) | Hard coating film | |
| JP7154738B2 (en) | transparent laminate | |
| CN109312012B (en) | Active energy ray-curable composition and film using same | |
| JP6953682B2 (en) | Urethane (meth) acrylate resin and laminated film | |
| EP2980163B1 (en) | Coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |