Technical field
[0001]
　The present invention relates to a laminate having a hydrophilic and antifogging.
BACKGROUND
[0002]
　Recently, organic materials such as plastics, and haze of the substrate to be formed of an inorganic material such as glass, there has been an increasing improvement demand for contamination.
[0003]
　As a method for solving the fogging problem, reactive surfactant, by antifogging coating containing an acrylic oligomer, a hydrophilic, a method of improving the water absorption has been proposed (e.g., see Non-Patent Document 1.). As a means for solving the contamination problem by improving the hydrophilicity of the material surface, float was a method of removing has been proposed by watering or rain stains such as outside air hydrophobic substance adhering to the outer wall or the like (e.g., see non-Patent documents 2 and 3.).
[0004]
　Further, the hydrophilic monomer by irradiation by controlling the amount of ultraviolet irradiation was applied a crosslinkable polymerizable monomer composition to a surface of a substrate to form a incompletely polymerized crosslinked polymer, then coating with ultraviolet again hydrophilic monomer hydrophilic material obtained by block polymerization or graft polymerization has been proposed in the surface of the crosslinked polymer (Patent documents 1 and 2).
[0005]
　However, the hydrophilic monomer to a simple substrate surface of the above hydrophilic material obtained by the method of block polymerization or graft polymerization, for hydrophilic group exists only on the surface, the long-term use low durability I had a problem which can not endure.
[0006]
　Further anionic compound having a hydrophilic group and a hydrophilic material obtained by using a ethanolamines hydrophilic obtained by using a (Patent Document 3), and the compound having a non-neutralized anionic hydrophilic group and an inorganic colloid sol sex material (Patent Document 4) it has been proposed. However, the hydrophilic material obtained by a method using ethanol amine, there are problems such as difficult to be hydrophilic or sticky surface by ethanolamine itself remaining inside the film, while the anionic unneutralized the hydrophilic material obtained by the method of using a compound having a hydrophilic group, also transparency hardly hydrophilized had problems such as easily lowered.
[0007]
　The present inventors, as a means for solving the above problems, inclined to a particular anionic hydrophilic groups are the membrane surface from the internal membrane (segregation), previously a laminate anionic hydrophilic group in the vicinity of the surface is present at high concentrations It has been proposed (Patent documents 5 to 11).
[0008]
　According to these methods, to solve the above problems, hydrophilic, anti-fogging properties, antifouling properties, scratch resistance, and a transparency superior crosslinked resin film and the laminated body is obtained. However, glasses, goggles, window glasses, mirrors, displays, among the transparent members applications commonly antifogging property such as the headlamp is required, there is a scene where extremely high antifogging property is required in a part, the the inventors of the extremely high antifogging even with the film and laminate of a crosslinked resin of proposals have in some cases sufficient response is not to the scene as required.
[0009]
　For example, when using the anti-fog layer of a general water-type surface (the surface touching the outside air) as the anti-fogging material, although while absorbing moisture is good without fog, high fluid as bathroom use There has been well known to lose antifogging in a relatively short time will not be able to water and immediately saturated in situations that are continuously supplied to the surface. On the other hand, when the present inventors have used the proposed hydrophilic material to the surface, it is possible to impart antifogging properties by suppressing the scattering of light for spreads even if moisture adheres by condensation or the like. Such hydrophilic materials, a variety of applications (glasses, goggles, window glasses, mirrors, displays, headlamps, etc.) long can be used, antifogging in very early moisture begins to adhere (hereinafter, "initial in some cases, anti-fogging property ") is not sufficient. This initial anti-fogging problems have been improved by the proposal of the present inventors (Patent Document 12) also.
[0010]
　However, in some cases it is difficult to maintain the initial anti-fogging semipermanently. For example, the surface anti-fogging property is lowered by wiping with a cloth or the like, if the moisture by condensation or the like adheres, further was also uneven water film formed as moisture adhering is wet and spread on the surface result, there may reduce the visibility when used in, for example, glasses, and the like. Furthermore, there is also a scene which is also required a high scratch resistance hard coating comparable to be applied to transparent materials, require both strong surface (scratch resistance comparable hard coat) high antifogging property (initial and long) It was still remain points to be improved for application to applications which.
CITATION
Patent Document
[0011]
Patent Document 1: JP 2001-98007 JP
Patent Document 2: JP 2011-229734 Patent Publication
Patent Document 3: JP 55-90516 Patent Publication
Patent Document 4: JP 2005-187576 Patent Publication
Patent Document 5: International Publication No. 2007/064003 discloses
Patent Document 6: WO 2013/014733 Patent Publication
Patent Document 7: WO 2015/178248 Patent Publication
Patent Document 8: WO 2015/087810 Patent Publication
Patent Document 9: WO 2013/054877 Patent Publication
JP 10: WO 2014/168122 Patent Publication
JP 11: WO 2016/017619 Patent Publication
JP 12: WO 2013/187311 Patent Publication
Non-patent literature
[0012]
Non-Patent Document 1: Dong Aki Synthesis Report, TREND 1999, February, 39 to 44
Non-Patent Document 2: Polymer, 44 (5), 307
Non-Patent Document 3: material of the future, 2 (1), 36- 41
Summary of the Invention
Problems that the Invention is to Solve
[0013]
　The present invention, we have a key challenge that the hydrophilic groups previously proposed to impart a higher anti-fogging property to the hydrophilic material consisting of segregated crosslinked resin to the surface.
Means for Solving the Problems
[0014]
　The present inventors have made intensive studies to solve the above problems, a hydrophilic layer having a high abrasion resistance made of a crosslinked resin having a hydrophilic group is segregated on the surface layer of the (A) (hydrophilic cured product and the substrate passing the laminated water-absorbing layer comprising a crosslinked resin (B), surprisingly, cause a is moisture near the surface (water vapor) is the hydrophilic layer of cloudiness (a) having new high water absorption during) the and by finding that it is water in the water-absorbing layer (B) and has led to dramatically improve the superior left antifog maintaining the scratch resistance. The crosslinked hydrophilic layer comprising the resin (A) and the water-absorbing layer due to water absorption and heat by appropriately designing the cross-linked structure of the water-absorbing layer laminated between the substrate (B) (B) its expansion destruction and interface also found that by controlling the release can be maintained a good appearance. Even more surprisingly, by also find that the use of the impact-resistant laminate of the present invention can also be improved, transparency, scratch resistance, fog resistance, and the invention laminate which is excellent in impact resistance can be obtained It has been reached.
[0015]
　That is, the present invention relates to the following [1] to [7].
[0016]
　[1]
　on the base material, water-absorbing layer (B) and hydrophilic layer (A) and are provided in this order,
　it said hydrophilic layer (A) has an anionic, cationic or nonionic hydrophilic groups, It consists crosslinked resin, and the inclination of the hydrophilic group in its hydrophilic layer (a) (hydrophilic group strength in the thickness 1/2 point of the hydrophilic layer (a) hydrophilic group intensity / hydrophilic layer on the surface (a)) is 1. 1 or more,
　the water-absorbing layer (B) is a laminate unit mass (g) water absorption rate per consists 5 ~ 500 wt% of the range of the crosslinked resin.
[0017]
　[2]
　The water-absorbing layer (B) is the [1] The laminate according comprising a crosslinked resin of a polymerizable composition comprising a compound represented by the following general formula (1).
[0018]
[Formula 1]

[0019]
(In the formula (1), B represents an organic group containing a polymerizable functional group represented by the following general formula (B), A is represented by the following general formula (A-1) ~ (A-18) represents any of the organic radical, a represents the number of organic groups B are attached to an organic radical a, in the range from 2 to 103. FIG.)
[0020]
[Formula 2]

[0021]
(Expressed in the formula (B), R, the R 'and R' 'are each independently a hydrogen atom or a methyl group, b represents 0 or 1, n represents an integer of 0 to 100, and **, organic to a terminal for coupling to the group a.)
[0022]
[Formula 3]

[0023]
(In the formula (A-1), m represents an integer of 1 ~ 20, R 1 and R 2 represents a hydrogen atom or a methyl group independently, and when m is 2 or more R 1 each other and R 2 each other each may be the same or different, O * represents the oxygen atom bonded to an organic group B.)
[0024]
[Chemical Formula 4]

[0025]
(In the formula (A-2), l represents an integer of 1 ~ 100, R 1 ~ R 4 represents a hydrogen atom or a methyl group independently, l is 2 or more when R 1 and between R 2 each other each may be the same or different, O * represents the oxygen atom bonded to an organic group B.)
[0026]
[Formula 5]

[0027]
(In the formula (A-3), l represents an integer of 1 ~ 100, R 1 ~ R 6 represents a hydrogen atom or a methyl group independently, l is 2 or more when R 1 together, R 2 to each other, and R 3 to each other may be the same or different, O * represents the oxygen atom bonded to an organic group B.)
[0028]
[Formula 6]

[0029]
(In the formula (A-4), l represents an integer of 1 ~ 100, R 1 ~ R 8 is a hydrogen atom or a methyl group independently, l is 2 or more when R 1 together, R 2 to each other, R 3 together, and R 4 together may be the same as or different from each other, O * represents the oxygen atom bonded to an organic group B.)
[0030]
[Chemical Formula 7]

[0031]
(In the formula (A-5), k represents an integer of 0 ~ 3, R # are each independently CH 2 , CH * or CHCH 2 O * represents, CH * is a CH group bonded to an organic radical B represents, O * represents the oxygen atom bonded to an organic group B.)
[0032]
[Formula 8]

[0033]
(In the formula (A-6), m 0100 represents an integer of 0 ~ 100, V 1 and V 2 each independently OH or O * represents, m 0100 V when is 2 or more 2 each other in the same It may be different, O * represents the oxygen atom bonded to an organic group B.)
[0034]
[Formula 9]

[0035]
(In the formula (A-7), m 010 0 represents an integer of ~ 10, V 1 and V 2 each independently OH or O * represents, W 1 and W 2 are each independently a hydrogen atom, methyl, OH or O * represents, m 010 is 2 or more when V 2 and between the W 2 to each other may be the same as or different from each other, O * represents the oxygen atom bonded to an organic group B.)
[0036]
[Formula 10]

[0037]
(Formula (A-8) in, R 1 and R 2 represents a hydrogen atom or a methyl group independently, O * represents the oxygen atom bonded to an organic group B.)
[0038]
[Of 11]

[0039]
(In the formula (A-9), n 26 represents an integer of 2 ~ 6, O * represents the oxygen atom bonded to an organic group B.)
[0040]
[Chem. 12]

[0041]
(In the formula (A-10), O * represents the oxygen atom bonded to an organic group B.)
[0042]
[Formula 13]

[0043]
(In the formula (A-11), n 28 represents an integer of 2 ~ 8, O * represents the oxygen atom bonded to an organic group B.)
[0044]
[Formula 14]

[0045]
(In the formula (A-12), O * represents the oxygen atom bonded to an organic group B.)
[0046]
[Formula 15]

[0047]
(In the formula (A-13), n 26 represents an integer of 2 ~ 6, O * represents the oxygen atom bonded to an organic group B.)
[0048]
[Chemical Formula 16]

[0049]
(In the formula (A-14), O * represents the oxygen atom bonded to an organic group B.)
[0050]
[Formula 17]

(In the formula (A-15), O * represents the oxygen atom bonded to an organic group B.)
[0051]
[Chem. 18]

[0052]
(In the formula (A-16), O * represents the oxygen atom bonded to an organic group B.)
[0053]
[Of 19]

[0054]
(In the formula (A-17), * - indicates a terminal for coupling to an organic radical B.)
[0055]
[Of 20]

[0056]
(In the formula (A-18), NH *
　. Representing the NH group bonded to an organic radical B is) [3]
　The compound represented by the general formula (1) is represented by the following general formula (2) (meth) the acrylate [2] the laminate according.
[0057]
[Of 21]

[0058]
(In the formula (2), k represents an integer of 0 ~ 3, R 1 ~ R 6 independently represent a hydrogen atom or a methyl group, m 1 and n 1 represents an integer of independently 0-100. )
　[4]
　wherein the water-absorbing layer (B),
　the comprising a crosslinked resin of a polymerizable composition comprising a compound represented by the general formula (1), and the following inorganic fine diameter 10 [mu] m [2] or [3 laminate according to].
[0059]
　[5]
　The linear expansion coefficient difference between the hydrophilic layer and (A) and the water absorbing layer (B) is 0 ~ 300 × 10 -6 as claimed in any one of the ranges / K [1] ~ [4] laminate.
[0060]
　[6]
　The hydrophilic layer (A) and the water-absorbing layer (B) the difference in linear expansion coefficient between the is 0 ~ 160 × 10 -6 laminate according to any one of a range of / K [1] to [4] body.
[0061]
　[7]
　The laminate according to any one of the applications is an optical article [1] to [6].
　[8]
　The optical article is an optical film, optical disc, optical lenses, spectacle lenses, eyeglasses, sunglasses, contact lenses, goggles, helmet shields, headlamp, the is any one selected from the group consisting of the tail lamp [7] laminate according.
Effect of the invention
[0062]
　According to the present invention, it is possible to provide a laminate excellent in antifogging property not hydrophilic only.
BRIEF DESCRIPTION OF THE DRAWINGS
[0063]
[1] Figure 1 In the examples, is a schematic diagram showing a method of sample preparation for measuring the inclination of the hydrophilic group concentration (Sa / Da).
DESCRIPTION OF THE INVENTION
[0064]
　[Laminate]
　The laminate of the invention has on a substrate, the water-absorbing layer (B) and hydrophilic layer (A) and are provided in this order. That is, the laminate of the present invention includes a substrate, water absorbing layer (B), and a structure containing a hydrophilic layer and (A) in this order.
[0065]
　
　hydrophilic layer constituting the laminate of the present invention (A) is formed by a crosslinked resin having an anionic, cationic or nonionic hydrophilic groups. In this hydrophilic layer (A), the ratio of the hydrophilic group strength of the hydrophilic layer (A) surface, and hydrophilic groups strength in the thickness 1/2 point of the hydrophilic layer (A) is 1.1 or more. In the present invention, the ratio is preferably 1.2 or more, more preferably 1.3 or more. In this specification, will be such a ratio is referred to as "inclination of hydrophilic groups".　　　
[0066]
　 Hydrophilic group
　Examples of the anionic hydrophilic group, for example, a sulfo group, a carboxyl group, a phosphoric acid group, O- sulfate groups (-O-SO 3 - ), and N- sulfate group (-NH-SO 3 - ) and the like and the like. Among these anionic hydrophilic groups, a sulfo group, a carboxyl group, and a phosphoric acid group is preferable. In the present invention, among these anionic hydrophilic groups, a sulfo group, and a phosphoric acid group are particularly preferred.
[0067]
　Here, the anionic hydrophilic group may be in the form of a free acid, or may have a form of a salt with a suitable cation. Such cation, ammonium ion, alkali metal ion, and an alkaline earth metal ion.
[0068]
　On the other hand, examples of the cationic hydrophilic group, for example, quaternary ammonium groups, betaine groups, and the like amine oxide groups. Among these cationic hydrophilic groups, preferably quaternary ammonium groups and betaine groups, in the present invention, particularly preferred quaternary ammonium group.
[0069]
　Examples of the nonionic hydrophilic group include a hydroxyl group, such as an ether group. Among these nonionic hydrophilic group is preferably a hydroxyl group.
[0070]
　Here, as the hydroxyl group, as long as the effect of the present invention, alcoholic hydroxyl group, may be any of a phenolic hydroxyl group, alcoholic hydroxyl group is preferable. Incidentally, in the above-mentioned anionic hydrophilic group, a sulfo group, there is a case that contains the partial structure represented by the form "-OH" such as phosphoric acid group and a carboxyl group, in the present invention, the "-OH" that are part of the anionic hydrophilic group such are not considered to be "hydroxyl group".
[0071]
　 Examples of the hydrophilic layer (A)
　in the present invention, anionic, inclination of cationic or nonionic hydrophilic group, (hydrophilic group strength of the hydrophilic group intensity / hydrophilic film center of the hydrophilic film surface) is 1.1 or more hydrophilic layer comprising any of the crosslinked resin as long as the hydrophilic layer comprising a crosslinked resin (a) (a) may also. Among the hydrophilic groups in their cross-linked resin is inclined towards the surface (segregation) and hydrophilic layer (A), obtained by curing the WO 2007/064003 (Patent Document 5) The composition according crosslinking a hydrophilic layer comprising an resin (a), the hydrophilic layer comprising an crosslinked resin obtained by curing the composition of WO 2013/014733 (Patent Document 6) (a), WO 2015/178248 discloses ( hydrophilic consisting Patent hydrophilic layer comprising a crosslinked resin obtained by curing the composition of the document 7) (a), WO 2015/087810 discloses (obtained by curing the composition of Patent Document 8) crosslinking resin layer (a), a hydrophilic layer comprising a crosslinked resin obtained by curing the composition of WO 2013/054877 (Patent Document 9) (a), WO 2014/168122 (Patent statement A hydrophilic layer comprising an crosslinked resin obtained by curing the composition of 10) (A), and a hydrophilic layer comprising an crosslinked resin obtained by curing the composition of WO 2016/017619 (Patent Document 11) either (a) it is preferred.
[0072]
　A hydrophilic layer hydrophilic group obtained by curing the composition of Patent Documents 5 to 11 is made inclined (segregated), crosslinked resin (A), two or more compositions which said hydrophilic layer (A) is obtained mixing may be laminated in a single layer, or only the composition one may be laminated in a single layer, or may be a multilayer laminated one by each one layer of two or more compositions.
[0073]
　The types of the hydrophilic group in the hydrophilic group inclined hydrophilic layer made of (segregated) was cured resin (A), the anionic hydrophilic group, a cationic hydrophilic group or a combination any or two or more nonionic hydrophilic groups, may, but anionic hydrophilic group or a cationic hydrophilic group is preferable as easily hydrophilic group more hydrophilic is increased, most preferred anionic hydrophilic group among them. Examples of the anionic hydrophilic group, a carboxyl group, a phosphoric acid group, and a sulfo group are preferred, and most preferably a sulfo group. Among these.
[0074]
　To mention more preferred form in the proposal of the present inventors, for example, WO 2007/064003 discloses the use of hydrophilic monomer composition (Patent Document 5) and WO 2015/087810 discloses ( hydrophilic layer obtained from a patent document 8) (a), WO 2013/054877 (Patent Document 9 using a hydrophilic polymer in the composition), WO 2014/168122 (Patent Document 10), and international hydrophilic layer obtained from Publication No. 2016/017619 (Patent Document 11) (A) can be mentioned. More preferably WO 2014/168122 discloses the use of hydrophilic polymer in the composition (Patent Document 10) and a hydrophilic layer obtained from WO 2016/017619 (Patent Document 11) (A).
[0075]
　 The method of forming the hydrophilic layer (A)
　the hydrophilic layer as described above (A) is an anionic, cationic, or a polymerizable composition that corresponds to the cross-linked resin having nonionic hydrophilic groups, was applied to a suitable surface it can be obtained by polymerizing curing. Here, the polymerizable composition causes a crosslinking reaction between molecules contained in the composition, as a result transitions from a liquid state to a solid state, a cured resin.
[0076]
　In one exemplary embodiment of the present invention, this polymerizable composition, as described in Patent Documents 5-8, anionic, cationic or nonionic hydrophilic group and (meth) acryloyl group, a compound having a functional group having a carbon-carbon double bond polymerizable carbon - - polymerizable carbon etc. are included a compound having 2 or more functional groups having a carbon-carbon double bond. In this embodiment, the polymerization curing, irradiation such as UV irradiation, or may be performed by heating. In this case, the polymerizable composition prior to polymerization curing, conventionally known photopolymerization initiator or thermal polymerization initiator may be added as appropriate.
[0077]
　In another exemplary embodiment of the present invention, this polymerizable composition, as disclosed in Patent Documents 9-11, a polymer having a hydrophilic group and an epoxy group, a silanol group or silanol group and generating functional groups are included. In this embodiment, the polymerization curing is carried out through the crosslinking reaction by reaction of epoxy group and a silanol group contained in the polymer. Here, the "generation functional groups silanol group", Si-O-R (R is an alkyl group), Si-X (X is a halogen atom) include functional groups and the like, silanol by hydrolysis give to the group. Silanol groups or generated functional groups silanol group, as described in Patent Document 9, may be present in different silane compounds and a polymer having a hydrophilic group and an epoxy group, JP 10 and 11, as described in, has may be contained in a polymer having a hydrophilic group and an epoxy group, or, with the "another silane compound", and a hydrophilic group and an epoxy group it may be included in both the polymer. Here, the "polymer having a hydrophilic group and an epoxy group" polymerizable carbon and hydrophilic group - functional compound having a group, polymerizable carbon and epoxy groups having a carbon-carbon double bond - carbon double bond it can be obtained by copolymerizing a mixture comprising a compound having a functional group having a. At this time, as described in Patent Documents 10 and 11, to the mixture, polymerizable carbon silanol groups or "silanol group-forming functional group of" - compounds having a functional group having a carbon-carbon double bond It may be carried out copolymerization in a state in which also contained, in this case, and a hydrophilic group, an epoxy group, so that the polymer having a silanol group or a "silanol group and capable of producing functional group" is obtained.
[0078]
　In either embodiment, the polymerizable preferably contain solvent to the composition, this solvent, SP value (solubility parameter sigma) is preferably 8.4 (cal / cm 3 ) 1 / 2 or more, more preferably 9.0 (cal / cm 3 ) 1/2 is desirable to include more solvents. If it contains a solvent in the polymerizable composition, after the coating, prior to said polymerization curing, it is preferred that the step of solvent removal is carried out.
[0079]
　In this specification, the polymerizable composition such as these are called for distinction between the polymerizable composition for later-described water-absorbing layer (B) "polymerizable composition for a hydrophilic layer (A)" Sometimes.
[0080]
　Hydrophilic group is inclined (i.e., hydrophilic groups strength of the hydrophilic group intensity / hydrophilic film center of the hydrophilic membrane surface at a 1.1 or higher) a method for forming a hydrophilic layer comprising a crosslinked resin (A), a representative method It is set forth below.
[0081]
　The hydrophilic layer (A), for example, can be obtained by cross-linking a layer composed of a copolymer having at least one group and a sulfo group selected from epoxy group and alkoxysilyl group.
[0082]
　Such copolymers typically comprise a structural unit represented by the following general formula (2a) and at least one constitutional unit represented by the following general formula of the structural units represented by (3a) (1a) copolymer (i) are exemplified.
[0083]
[Formula 22]

[0084]
　The formula (1a), in (2a) and (3a), in the case of a + b + c = 1, a, b, and c represents the structural unit ratio of the respective structural units, a = 0 ~ 1, b = 0 ~ 1 a = 0 ~ c
1, a 1 represents a single bond, a divalent hydrocarbon group of 1 to 10 carbon atoms, a group represented by the following formula (1-1) or the following formula (1-2 ) represents a group represented by, a 2 represents a single bond, a divalent hydrocarbon group of 1 to 10 carbon atoms, a group represented by the following formula (2-1) or the following formula (2-2 ) represents a group represented by, a 3 represents a single bond, a divalent hydrocarbon group of 1 to 10 carbon atoms, a group represented by the following formula (3-1) or the following formula (3-2 ) represents a group represented by,
R 1 , R 2 , and R 3 each independently represent a hydrogen atom or a methyl group, R 4 each is a hydrogen atom, a methyl group, an ethyl group, a propyl group or, Indicates methyl group, R 10 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group or butoxy group,,
M is a hydrogen atom, an alkali metal ion, 1/2 valent alkaline earth metal ions, indicates an ammonium ion or an amine ion;
formula (1-1), (1-2), (2-1), (2-2), (3-1), and in (3-2), n and n 2 is an integer from 1 to 10 independently, n 1 is an integer of 0 ~ 10, m is an integer of 1 to 6, m 1 is 0 to 6 of an integer, l is an integer of 0 ~ 4, R 5 and R 6 represents a hydrogen atom or a methyl group independently, * is SO 3 end on the side that binds to M, ** epoxy group end on the side that bind, *** indicates the end of the side bonded to Si atoms.
[0085]
[Of 23]

[0086]
　Among the above copolymer (i), a copolymer comprising a structural unit represented by the general formula (1a) and (2a) (i1), the general formula (1a), (2a), and (3a) copolymer containing a constituent unit represented in (i3) is a preferred aspect.
[0087]
　As the copolymer (i), a copolymer comprising a structural unit represented by the following general formula (4a) and (5a) (i1-1), the following general formula (4a), and (5a) (6a copolymer containing a constitutional unit represented by) (i3-1) are further preferred embodiment.
[0088]
[Of 24]

[0089]
　The formula (4a), in (5a) and (6a), in the case of a + b + c = 1, a, b, and c represents the structural unit ratio of the respective structural units, a = 0 ~ 1, b = 0 ~ 1 a c = 0 ~ 1,
n is an integer of 1 ~ 10, n 1 is an integer of 0 ~
10, R 1 , R 2 , R 3 , R 5 , and R 6 are each independently represents a hydrogen atom or a methyl group, R 4 are each a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group,, R 10 is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group represents ethoxy group, a propoxy group or butoxy group,,
M represents a hydrogen atom, an alkali metal ion, 1 / bivalent alkaline earth metal ions, ammonium ions, or an amine ion.
[0090]
　The copolymer (i) are, for example, the following formula and at least one compound selected from compounds represented by a compound represented by and the following formula in (2'a) (3'a), the following formula (1 ' obtained by copolymerizing a compound represented by a).
[0091]
[Of 25]

[0092]
　In the above formula (1'a), R 1 , A 1 , and M have the same meanings as the above formula (1a).
[0093]
[Of 26]

[0094]
　In the above formula (2'a), R 2 and A 2 have the same meanings as the above formula (2a).
[0095]
[Of 27]

[0096]
　In the above formula (3'a), R 3 , R 4 , R 10 and A 2 have the same meanings as the above formula (3a).
[0097]
　Among the compounds represented by the above formula (1'a), (meth) sulfonic acid compound having an acrylamide group are preferred, compounds represented by the following general formula (4'a) is more preferable.
[0098]
[Formula 28]

[0099]
　In the above formula (4'a), R 1 , R 5 , R 6 , M, and n 1 have the same meanings as the above formula (4a).
[0100]
　Among the compounds represented by the above formula (2'a), (meth) epoxy compounds are preferred having an acryloyloxy group, a compound represented by the following general formula (5'a) is more preferable.
[0101]
[Of 29]

[0102]
　In the above formula (5'a), R 2 , and n have the same meanings as the above formula (5a).
[0103]
　Among the compounds represented by the above formula (3'a), (meth) acrylate dialkoxysilane compounds are preferred having acryloyloxy group, a compound represented by the following general formula (6'a) is more preferable.
[0104]
[Formula 30]

[0105]
　In the above formula (6'a), R 3 , R 4 , R 10 , and n have the same meanings as in the formula (6a).
[0106]
　Examples of the compound represented by the above formula (4'a), 1- (meth) acrylamide - methanesulfonic acid, 1- (meth) acrylamide - potassium methanesulfonic acid, 2- (meth) acrylamido - ethanesulphonic acid, 2 - (meth) acrylamide - sodium ethanesulfonic acid, 2- (meth) acrylamido - propanesulfonic acid, 2- (meth) acrylamide - potassium propanesulfonic acid, 2- (meth) acrylamido-2-methyl - propanesulfonic acid (( meth) acrylamide -t- butyl sulfonic acid), 2- (meth) acrylamido-2-methyl - propanesulfonic acid sodium salt, 2- (meth) acrylamido-2-methyl - potassium propanesulfonic acid salt, 2- (meth) acrylamido-2-methyl - propanesulfonic acid rubidium salt , 2- (meth) acrylamido-2-methyl - propanesulfonic acid calcium salt, 2- (meth) acrylamido-2-methyl - propanesulfonic acid magnesium salt, 2- (meth) acrylamido-2-methyl - propyl sulfonic acid ammonium salt, 3- (meth) acrylamides - such as sulfonic acid compounds having a (meth) acryloyl amide group, such as potassium-propanesulfonic acid salt.
[0107]
　Examples of the compound represented by the above formula (5'a), for example, glycidyl - (meth) acrylate, epoxy - (meth) acrylate, 2-glycidyloxy - ethyl - (meth) acrylate, 3-glycidyloxy - propyl - (meth) acrylate, 4-glycidyloxy - butyl - (meth) acrylate, 6-glycidyloxy - hexyl - (meth) acrylate, 5-glycidyloxy-3-oxapentyl - (meth) acrylate, 3-glycidyloxy -2 - hydroxy - propyl - (meth) acrylate, 2,3-bis (glycidyloxy) - propyl - (meth) acrylate, trimethylolpropane - diglycidyl ether - (meth) acrylate, {4- glycidyloxyphenyl} - {( 4- (meth) acryloyloxy -3 - hydroxy-1-oxabutyl) phenyl} -2,2-propane, 7-glycidyloxy-6,6-dimethyl-2-hydroxy-4-oxa-heptyl - (meth) acrylate.
[0108]
　Examples of the compound represented by the above formula (6'a), for example, (meth) acryloyloxy - ethyltrimethoxysilane, (meth) acryloyloxy - propyl - trimethoxysilane, (meth) acryloyloxy - butyl - trimethoxy silane, (meth) acryloyloxy - hexyl - trimethoxysilane, (meth) acryloyloxy - decyl - trimethoxysilane, (meth) acryloyloxy - propyl - triethoxysilane, (meth) acryloyloxy - propyl - tripropoxysilane, (meth) acryloyloxy - propyl - tributoxy silane, (meth) acryloyloxy - propyl - methyl dimethoxy silane, (meth) acryloyloxy - like ethyldiethoxysilane - propyl.
[0109]
　The copolymer weight average molecular weight standard polymethyl methacrylate equivalent by gel permeation chromatography (GPC) of (i) (Mw) is preferably in the range of 500 to 3,000,000.
[0110]
　Further, the hydrophilic layer (A) is selected from amino resins represented by the following general formula (7a) (ii), silane compounds represented by the following general formula (11a) (iii), and inorganic particles (iv) at least one, can be prepared by cross-linking a layer formed of a composition comprising the above copolymer (i).
[0111]
[Of 31]

[0112]
　In the above formula (7a), R 30 is a hydrogen atom, an alkyl group, hydroxymethyl group or alkoxymethyl group having 1 to 10 carbon atoms, from 1 to 10 carbon atoms, R 40 represents a hydroxyl group, a hydrogen atom, a carbon an alkyl group having 1 to 10, or an alkoxy group having 1 to 10 carbon atoms, Q190 is an integer from 1 to 90, mother MC is represented by any one of the following formulas (8a) ~ (10a) represents nuclear, # 2 is a bond that binds to the # 1 in the following general formula formula (8a) ~ (10a), the number of the # 1 and # 2 are identical;
in the following formula (8a), q 030 is an integer from 0 to 30, respectively, q 030 may be the same or different, R 30 and R 40 are the same as defined in formula (7a),
in the following formula (9a), q 050 is an integer of 0 ~ 50, X represents an oxygen atom or a sulfur atom, R 30 and R 40 are the same as defined in formula (7a),
in the following equation (10a), q 050 is an integer of 0 to 50.
[0113]
[Formula 32]

[0114]
[Formula 33]

[0115]
[Formula 34]

[0116]
[Formula 35]

[0117]
　In the above formula (11a), X 1 and X 2 are each independently a hydroxyl group, an alkoxy group or a halogen atom, having 1 to 4 carbon
atoms, R 11 ~ R 14 are each independently a hydroxyl group, hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, an allyl group, a phenyl group, 2-phenyl - ethyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom,, q is an integer of 0-10000 it is.
[0118]
　The inorganic particles (iv) is, for example, silver particles, copper particles, copper oxide particles, silica particles, hollow silica particles, alumina particles, iron oxide particles, cobalt oxide particles, dioxide zirconia particles, titanium dioxide particles, antimony oxide particles etc. the. These inorganic particles are also included inorganic particles modified with an organic group having an alkyl group or a (meth) acryloyl groups of the surface for the purpose of improving the dispersibility. Further, below the section "inorganic fine particles" in the "composition of the polymerizable composition," "water-absorbing layer (B)" subsection in also mentioned as the inorganic particles (iv). Description of the case where the "inorganic fine particles" are included as the inorganic particles (iv) is described later in later sections "composition of the polymerizable composition" subsection of the "water-absorbing layer (B)" in.
[0119]
　The cured product, when is obtained from a composition comprising an amino resin (ii) and copolymer (i) is included in the composition, the copolymer (i) and the amino resin (ii ) and the weight ratio of (i) / (ii) is preferably in the range of 99 / 1-1 / 99.
[0120]
　The cured product, an amino resin (ii), inorganic particles (iv), and if those obtained from a composition comprising a copolymer (i), included in the composition, the copolymer ( i), the total by weight to 100 parts by weight of the copolymer (i) 5 ~ 98 parts by weight, an amino resin (ii) 1 ~ 70 parts by weight of the amino resin (ii) and inorganic particles (iv), and inorganic particles (iv) 1 ~ it is preferably contains 90 parts by weight.
[0121]
　The cured product, when the silane compound (iii) is obtained from a composition comprising a copolymer (i) is included in the composition, the weight and the silane compound in the copolymer (i) SiO and (iii) 2 ratio of the reduced weight (i) / (ii) is preferably in the range of 99.9 / 0.1-0.1 / 99.9, 99 / 1-1 / more preferably in the range of 99, more preferably as long as the range of 90 / 10-10 / 90.
[0122]
　Crosslinked copolymer resin (i) or, amino resin (ii), the silane compound (iii), and at least one copolymer selected from the inorganic particles (iv) (i) and crosslinked resin of a composition comprising the can be prepared, for example, by copolymer (i) or heating said composition (i.e. thermosetting).
[0123]
　As the copolymer (i) or the composition further solubility parameter σ is 9.0 (cal / cm 3 ) 1/2 is is a preferred embodiment to use a mixture comprising more solvents. After providing a coating film made of a mixture containing such a solvent on the water-absorbing layer (B), by removing the solvent from the coating film by heating, the hydrophilic layer hydrophilic group segregated on the more superficial ( a) can be obtained.
[0124]
　Examples of the solvent include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol (1-amyl alcohol) primary alcohol and the like; and
1-methoxy-2-propanol (methoxypropanol), 2- methoxy-1-ethanol (methoxy ethanol) include alkoxy alcohols, such as 2-isopropoxy-1-ethanol.
[0125]
　Solubility parameter (SP value) can be easily calculated by a simple calculation method shown below.
[0126]
　Dissolution formula parameter sigma
1) per 1mol latent heat of vaporization
Hb = 21 × (273 + Tb ) ( unit: cal / mol), Tb: boiling point (°
C.) 2) the latent heat of vaporization per 1mol at 25 ° C.
H25 = Hb × { 1 + 0.175 × (Tb-25 ) / 100} ( unit: cal / mol), Tb: boiling point (°
C.) 3) intermolecular bonding energy E = H25-596 (unit: cal /
mol) 4) solvent 1 ml (cm 3 ) between molecules per binding energy
E1 = E × D / Mw (unit: cal / cm 3 ), D: density (g / cm 3 ), MW: molecular weight
5) solubility parameter (SP value) sigma = (E1) 1/2　(unit: Cal / Cm 3 ) 1/2
[0127]
　The thickness of the hydrophilic layer (A) is may properly determined depending on the use, usually 0.0001 ~ 500 [mu] m, preferably 0.05 ~ 500 [mu] m, more preferably 0.1 ~ 300 [mu] m, more preferably 0.5 ~ 100 [mu] m , even more preferably 1 ~ 50 [mu] m, particularly preferably from 2 ~ 30 [mu] m.
[0128]
　
　water layer constituting the laminate of the present invention (B), the unit mass (g) water absorption rate per consists 5 ~ 500 wt% of the range of the crosslinked resin. The water absorption layer (B) is located between the substrate to be described later with the hydrophilic layer (A). As used herein, "water absorption", vertical 0.5 ~ 1.5 cm, lateral 4.5 ~ 5.5cm, the resin piece initial weight of the thickness of 0.3 ~ 1.0 cm alpha, of 25 ° C. refers to a water absorption ratio defined by the weight of 24 hours was dipped in distilled water (weight after water absorption) beta and the time of (β-α) / α × 100).
[0129]
　The water absorption layer (B) is to improve the antifogging property by amazing water near the surface is passed through the hydrophilic layer of the surface (A) to absorb water by. Therefore, the laminate of the present invention, may further comprise a "other layers" described later, the water-absorbing layer (B) if located in any layer between the hydrophilic layer and (A) a substrate good, it is preferably closer to the hydrophilic layer of only the surface to enhance the water absorption capacity as possible in order to improve the antifogging property (a) from the surface, that have direct contact to the hydrophilic layer (a) most preferable.
[0130]
　Also, the higher the absorbency of the water absorbing layer (B) is to enhance the anti-fogging Preferably, specifically, the water absorption per the unit mass of the crosslinked resin constituting the water-absorbing layer (B) (g) there preferably in the range of 10 ~ 300 wt%, more preferably in the range of 20 ~ 200 wt%, and most preferably in the range of 30 ~ 150wt%.
[0131]
　In the present invention, the water-absorbing layer (B) is preferably the difference in linear expansion coefficient between the hydrophilic layer (A) is small to some extent. Here, when the water-absorbing layer (B) is not cross-linked resins such as linear polymers, water-absorbing layer by hygroscopic expansion (B) itself or broken, or the upper layer of the hydrophilic layer (A) linear to expansion difference increases with by some unfavorable tendency may or cracked in the hydrophilic layer (a). Water absorbing layer contrast (B) is preferably hardly occurs destruction or cracks as described above in the case of cross-linked resin. The difference in linear expansion coefficient between the hydrophilic layer (A) is 0 × 10 is in the water-absorbing layer consisting of crosslinked resin (B) -6 / K or 300 × 10 -6 water consisting / K or less in the range of crosslinked resins layer (B) is in the less preferred trend generation of cracks in the hydrophilic layer (a). Here, the upper limit of the linear expansion coefficient difference is preferably, 250 × 10 -6 / K, more preferably 200 × 10 -6 / K, more preferably 160 × 10 -6 is / K. These water-absorbing layer (B) may have a single layer may be two or more layers.
[0132]
　In order to minimize the generation of cracks in the hydrophilic layer (A), as described below, the laminate of the present invention, the hydrophilic layer below the buffer layer (C) (A) and water-absorbing layer (B) it is also preferred to have between.
[0133]
　Water absorbing layer (B) as preferably used crosslinked resin, for example, polyurethane resins, polythiourethane resins, polyurea resins, polyepoxy resins, polythioether epoxy resin, polyphenol resin, poly melamine resins, polyacrylic resins, polymethacrylic resins, including but common crosslinking resins such as polyolefin resins, polyacrylic resins and polymethacrylic resin is the preferred trend among these crosslinking resins.
Here combined polyacrylic and polymethacrylic poly (meth) acrylic, is expressed in by combining the acrylate and methacrylate (meth) below acrylate both.
[0134]
　Among these (meth) acrylic resin, obtained by curing the crosslinkable polymerizable composition comprising a compound having an ether group and a hydroxyl group and the molecule has two or more (meth) acrylate group-containing (meth) acrylate resins are preferable. Examples of the compound having an ether group and a hydroxyl group (meth) acrylate groups and 2 or more has and the molecule, the compound represented by the general formula (1) are preferred. In other words, in a preferred embodiment of the present invention, the water-absorbing layer (B), the polymerizable composition comprising a compound represented by the following general formula (1) (hereinafter, "polymerizable composition for water-absorbing layer (B) is preferably made of a crosslinked resin if there is.) called ".
[0135]
[Formula 36]

[0136]
　In the formula (1), the organic B represents an organic group containing a polymerizable functional group represented by the following general formula (B), A is represented by the following general formula (A-1) ~ (A-18) represents any of the radical, a represents the number of organic groups B are attached to an organic radical a, in the range from 2 to 103. FIG.
[0137]
[Formula 37]

[0138]
　Represents wherein (B), R, the R 'and R' 'are each independently a hydrogen atom or a methyl group, b represents 0 or 1, n represents an integer of 0 to 100, ** is an organic radical to a terminal for coupling to the a. Wherein said n is more preferably 1 to 100 integer, more preferably 5-80 integer, even more preferably from integer of 10-50.
[0139]
[Formula 38]

[0140]
　Wherein (A-1), m represents an integer of 1 ~ 20, R 1 and R 2 represents a hydrogen atom or a methyl group independently, and when m is 2 or more R 1 each other and R 2 together are each may be the same or different, O * represents the oxygen atom bonded to an organic radical B. Here, the m is preferably an integer of 2 to 10, more preferably as long as an integer of 2-6. If an organic group in which the A is represented by formula (A-1), examples of the compound represented by the formula (1), ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth ) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,5-neopentyl glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1,7-heptane diol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10 decanediol di (meth) acrylate, 1,2-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - Tan, 1,2-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - propane, 1,3-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - propane, 1,4-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - butane, bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - neopentane, 1,6-bis { 3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - hexane, 1,8-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - octane, 1,10-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - decane, 1,11-bis {3- (meth) acryloyloxy-2-hydrate Alkoxy - propyloxy} - dodecane, 1,12-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy} - undecane and 1,20- bis {3- (meth) acryloyloxy-2-hydroxy - propyloxy} - eicosane, and the like.
[0141]
[Of 39]

[0142]
　Wherein (A-2), l represents an integer of 1 ~ 100, R 1 ~ R 4 represents a hydrogen atom or a methyl group independently, when l is 2 or more R 1 each other and R 2 together are each may be the same or different, O * represents the oxygen atom bonded to an organic radical B. Wherein l in the formula (A-2) is preferably in the range of 1-50, more preferably in the range of 1 to 30, and more preferably it ranges from 0 to 20. If an organic group in which the A is represented by the general formula (A-2), examples of the compound represented by the formula (1), diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra ethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth ) acrylate, decamethylene glycol di (meth) acrylate, undecalactone ethylene glycol di (meth) acrylate, tetradecanol ethylene glycol di (meth) acrylate, Trichoderma Sa ethylene glycol di (meth) acrylate, pentaerythritol contour ethylene glycol di (meth ) Acrylate, f Kuta ethylene glycol di (meth) acrylate, 1,5-bis {3- (meth) acryloyloxy-2-hydroxy - propyl oxy} -3-oxa-heptane, 1,8-bis {3- (meth) acryloyloxy-2-hydroxypropyl - propyloxy}-3,6, 1,11-bis {3- (meth) acryloyloxy-2-hydroxy - propyl oxy} -3,6,9-trio key sound decane , di (1,2-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, tri (1,2-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, and the like.
[0143]
[Of 40]

[0144]
　Wherein (A-3), l represents an integer of 1 ~ 100, R 1 ~ R 6 represents a hydrogen atom or a methyl group independently, when l is 2 or more R 1 each other, R 2 to each other, and R 3 together may be the same or different, O * represents the oxygen atom bonded to an organic radical B. Wherein l in the formula (A-3) is preferably 1-50, more preferably in the range of 1 to 30, and more preferably ranges from 1 to 20. If an organic group in which the A is represented by the general formula (A-3), examples of the compound represented by the formula (1), di (1,3-propylene glycol) bis {3- (meth) acryloyl oxy-2-hydroxy - propyl ether}, tri (1,3-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, tetra (1,3-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, nona (1,3-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, tetradeca (1,3-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, Toriakonta (1,3 propylene glycol Call) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, ha (1,3-propylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, ethoxylated dodeca propylene glycol dimethacrylate, etc. ethoxylated dodeca propylene glycol diacrylate.
[0145]
[Formula 41]

[0146]
　Wherein (A-4), l represents an integer of 1 ~ 100, R 1 ~ R 8 is a hydrogen atom or a methyl group independently, when l is 2 or more R 1 s, R 2 s, R 3 with each other, and R 4 together may be the same or different, O * represents the oxygen atom bonded to an organic radical B. Wherein l in the formula (A-4) is preferably in the range of 1-50, more preferably in the range of 1 to 30, and more preferably ranges from 1 to 20. If an organic group in which the A is represented by the general formula (A-4), examples of the compound represented by the formula (1), di (1,4-butylene glycol) bis {3- (meth) acryloyl oxy-2-hydroxy - propyl ether}, tri (1,4-butylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, tetra (1,4-butylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, nona (1,4-butylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, tetradeca (1,4-butylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, Toriakonta (1,4-butylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, ha (1,4-butylene glycol) bis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, polytetramethylene glycol diacrylate and the like.
[0147]
[Formula 42]

[0148]
　Wherein (A-5), k represents an integer of 0 ~ 3, R # are each independently CH 2 , CH * or CHCH 2 O * represents, CH * represents CH group bonded to an organic radical B , O * represents the oxygen atom bonded to an organic radical B. Wherein k is in the range of 1-3 is preferred, more preferably in the range of 1-2, 1 being most preferred. If an organic group in which the A is represented by the general formula (A-5), as examples of the compound represented by the formula (1), 2-acryloxy deca-ethoxy-6-acryloxy-1,4,7 trioxatridecane triazacyclononane, 2-acryloxy-undecalactone ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy Sid deca-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy tridecane-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy tetradecane-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy pentadecane ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy-hexadecane-ethoxy-6-acryloxy-1,4,7 trioxadecyl cyclo Nonane, 2-acryloxy heptadecane-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryl Roxio Kuta decan-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acrylate Loki Shino Na decane-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy CHILLY co San-ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-acryloxy Heng equalize San ethoxy-6-acryloxy-1,4,7 trioxadecyl triazacyclononane, 2-methacryloxy-pentadecane-ethoxy-6-methacryloxy-1,4,7 trioxadecyl triazacyclononane and the like. In the present invention, among such compounds, particularly preferable ones include represented (meth) acrylate by the following general formula (2).
[0149]
[Chemical Formula 43]

[0150]
　Wherein (2), k represents an integer of 0 to 3, R 1 ~ R 6 independently represent a hydrogen atom or a methyl group, m 1 and n 1 represents an integer of 0 to 100 independently.
[0151]
　Incidentally, (meth) acrylate represented by the formula (2), in addition to the water-absorbing layer used in this application (B) also, in forming the effective space within the material or material which requires flexibility it can be used.
[0152]
[Formula 44]

[0153]
　Wherein (A-6), m 0100 represents an integer of 0 ~ 100, V 1 and V 2 each independently OH or O * represents, m 0100 V when is 2 or more 2 each other be the same or different well Te, O * represents the oxygen atom bonded to an organic radical B. Wherein m 0100 is preferably in the range of 0 to 30, more preferably in the range of 0 to 10, and more preferably ranges from 0-5. If an organic group in which the A is represented by the general formula (A-6), as examples of the compound represented by the formula (1), glycerin-1,3-di (meth) acrylate, (2,3 di (meth) acryloyloxy - propyloxy) diethylene glycol (meth) acrylate, (2,3-di (meth) acryloyloxy - propyloxy) triethylene glycol (meth) acrylate, (2,3-di (meth) acryloyloxy - propyloxy) tetraethylene glycol (meth) acrylate, (2,3-di (meth) acryloyloxy - propyloxy) octaethyleneglycol (meth) acrylate, (2,3-di (meth) acryloyloxy - propyloxy) tetradecanoyl ethylene glycol (meth) acrylate, (2,3-di (meth) acryloyloxy - propyloxy) Te Tiger contour ethylene glycol (meth) acrylate, diglycerol 1,7-di (meth) acrylate, diglycerol -1,2,7- tri (meth) acrylate, triglycerol 1,11-di (meth) acrylate, tetraglycerol -1,15- di (meth) acrylate, pentaglycerol -1,19- di (meth) acrylate, hexaglycerin -1,23- di (meth) acrylate, decaglycerol -1,39- di (meth) acrylate, triacontanyl glycerin -1,119- di (meth) acrylate, f Kuta glycerin -1,399- di (meth) acrylate, glycerol-1,2,3-tris {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, diglycerin -1,2,7- tris {3- (meth) acryloyloxy-2-hydroxy Propyl ether}, triglycerol -1,2,11- tris {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, triglycerol -1,6,11- tris {3- (meth) acryloyloxy - 2-hydroxypropyl - propyl ether}, triglycerol -1,2,6,11- tetrakis {3- (meth) acryloyloxy-2-hydroxy - propyl ether}, 1- (acryloxy - tetra co San ethoxy) -2,3 - Zia methacryloxy propane, 1- (acryloxy - pen octopus San ethoxy) -2,3-diaryl methacryloxy propane, 1- (acryloxy - hexa co San ethoxy) -2,3-diaryl methacryloxy propane, 1- (acryloxy - hepta Kosan'etokishi) -2,3-diaryl methacryloxy propane, 1- (acryloxy - octa co San ethoxy) -2,3 - Zia methacryloxy propane, 1- (acryloxy - Bruno Naco San ethoxy) -2,3-diaryl methacryloxy propane, 1,2,3-tri (acryloxy - polyethoxy) propane, 1- (methacryloxy - hepta co San ethoxy) -2 , 3-di methacryloxypropyltrimethoxysilane propane.
[0154]
[Formula 45]

[0155]
　Wherein (A-7), m 010 0 represents an integer of ~ 10, V 1 and V 2 each independently OH or O * represents, W 1 and W 2 are each independently a hydrogen atom, methyl group, OH or O * represents, m 010 is 2 or more when V 2 and between the W 2 may be different from each each other identical, O * represents the oxygen atom bonded to an organic radical B. Wherein m 010 is preferably in the range of 0 to 8, more preferably in the range of 0-6, and more preferably it ranges from 0-4. If an organic group in which the A is represented by the general formula (A-7), examples of the compound represented by formula (1), ethoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated such as pentaerythritol tetra acrylate.
[0156]
[Formula 46]

[0157]
　Wherein (A-8), R 1 and R 2 represents a hydrogen atom or a methyl group independently, O * represents the oxygen atom bonded to an organic radical B. If an organic group in which the A is represented by the general formula (A-8), examples of the compound represented by the formula (1), 2,2-bis - [4- (acryloxy - polyethoxy) phenyl] - propane, 2,2-bis - [4- (acryloxy - polyethoxy) phenyl] - propane, and the like.
[0158]
[Formula 47]

[0159]
　Wherein (A-9), n 26 represents an integer of 2 ~ 6, O * represents the oxygen atom bonded to an organic radical B. Wherein n 26 is preferably an integer of 2 to 4, more preferably when an integer of 2-3, most preferably if 2. If an organic group in which the A is represented by the general formula (A-9), as examples of the compound represented by the formula (1), 1,2-bis {3- (meth) acryloyloxy-2-hydroxy - such propyloxy} benzene.
[0160]
[Formula 48]

[0161]
　Wherein (A-10), O * represents the oxygen atom bonded to an organic radical B. If an organic group in which the A is represented by the general formula (A-10), as examples of the compound represented by formula (1), and the like ethoxylated benzene dimethanol diacrylate.
[0162]
[Formula 49]

[0163]
　Wherein (A-11), n 28 represents an integer of 2 ~ 8, O * represents the oxygen atom bonded to an organic radical B. Wherein n 28 is preferably an integer of 2 to 4, more preferably when an integer of 2-3, most preferably if 2. If an organic group in which the A is represented by the general formula (A-11), as examples of the compound represented by the formula (1), 2,6-di - (acryloxy - tetraethoxy) naphthalene, 1,5 - di - such as - (acryloxy tetraethoxy) naphthalene.
[0164]
[Of 50]

[0165]
　Wherein (A-12), O * represents the oxygen atom bonded to an organic radical B. If an organic group in which the A is represented by the general formula (A-12), as examples of the compound represented by the formula (1), 9,9-bis [4- (2-acryloyloxy ethoxy) phenyl] and fluorene and the like.
[0166]
[Formula 51]

[0167]
　Wherein (A-13), n 26 represents an integer of 2 ~ 6, O * represents the oxygen atom bonded to an organic radical B. Wherein n 26 is preferably an integer of 2 to 4, more preferably when an integer of 2-3, most preferably if 2. If an organic group in which the A is represented by the general formula (A-13), as examples of the compound represented by the formula (1), 1,2-bis {3- (meth) acryloyloxy-2-hydroxy - such propyloxy} cyclohexane.
[0168]
[Of 52]

[0169]
　Wherein (A-14), O * represents the oxygen atom bonded to an organic radical B. If an organic group in which the A is represented by the general formula (A-14), as examples of the compound represented by the formula (1), ethoxylated cyclohexanedimethanol diacrylate, etc. ethoxylated cyclohexanedimethanol dimethacrylate and the like.
[0170]
[Of 53]

[0171]
　Wherein (A-15), O * represents the oxygen atom bonded to an organic radical B. If an organic group in which the A is represented by the general formula (A-15), as examples of the compound represented by formula (1), and the like ethoxylated norbornane dimethanol diacrylate.
[0172]
[Formula 54]

[0173]
　Wherein (A-16), O * represents the oxygen atom bonded to an organic radical B. If an organic group in which the A is represented by the general formula (A-16), as examples of the compound represented by the formula (1), tricyclodecane dimethanol methacrylate, tricyclodecane diacrylate and the like.

The scope of the claims
[Requested item 1]
　On a base material, water-absorbing layer (B) and hydrophilic layer (A) and are provided in this order,
　said hydrophilic layer (A), a crosslinked resin having an anionic, cationic or nonionic hydrophilic groups, in it, and the inclination of the hydrophilic group in its hydrophilic layer (a) (hydrophilic group strength in the thickness 1/2 point of the hydrophilic layer (a) hydrophilic group intensity / hydrophilic layer on the surface (a)) is 1.1 or more There,
　the water-absorbing layer (B) is a laminate unit mass (g) water absorption rate per consists 5 ~ 500 wt% of the range of the crosslinked resin.
[Requested item 2]
　The water absorbing layer (B) is laminated body according to claim 1, wherein comprising a crosslinked resin of a polymerizable composition comprising a compound represented by the following general formula (1).
[Chemical formula 1]

(Equation (1), B is represented by the following general formula (represents an organic group containing a polymerizable functional group represented by B), A is represented by the following general formula (A-1) ~ (A -18) in represents any of the organic groups represented, a is represents the number of organic groups B are attached to an organic radical a, in the range from 2 to 103. FIG.)
[formula 2]

(in the formula (B), R, R 'and R' 'each independently represent a hydrogen atom or a methyl group, b represents 0 or 1, n represents an integer of 0 to 100, and **, the terminal for coupling to an organic radical a shown.)
[formula 3]

(in the formula (a-1), m represents an integer of 1 ~ 20, R 1 and R 2 represents a hydrogen atom or a methyl group independently, and when m is 2 or more R 1 and between R 2 may be different and each other respectively identical, O * represents the oxygen atom bonded to an organic group B.)
[Chemical formula 4]

(in the formula (a-2), l is an integer of from 1 to 100 a represents, R 1 ~ R 4 represents a hydrogen atom or a methyl group independently, l if R 2 or 1 to each other and R 2 may be different from each are between the same, O * represents the oxygen atom bonded to an organic group B .)
[Chemical formula 5]

(in the formula (a-3), l represents an integer of 1 ~ 100, R 1 ~ R 6 represents a hydrogen atom or a methyl group independently, and when l is 2 or more R 1 together, R 2 together, and R 3 together may be the same or different, O * represents the oxygen atom bonded to an organic group B.)
[formula 6]

(in the formula (a-4), l is 1 represents an integer of ~ 100, R 1 ~ R 8 is a hydrogen atom or a methyl group independently, l is 2 or more when R 1 together, R 2 together, R 3 together, and R 4 each other at each same may be different, O * is. indicative of an oxygen atom bonded to an organic group B)
[Chemical formula 7]

(in the formula (a-5), k represents an integer of 0 ~ 3, R # Each independently CH 2 , CH * or CHCH 2 O * represents, CH * represents CH group bonded to an organic group B, O * represents the oxygen atom bonded to an organic group B.)
[Formula 8]

(in the formula (a-6), m 0100 represents an integer of 0 ~ 100, V 1 and V 2 each independently OH or O * represents, m 0100 V when is 2 or more 2 each other in the same may be different, O * represents the oxygen atom bonded to an organic group B.)
[Chemical formula 9]

(in the formula (a-7), m 010 is an integer of 0 ~ 10, V 1 and V 2 , respectively independently OH or O * represents, W 1 and W 2 are each independently a hydrogen atom, a methyl group, OH or O * represents, m 010 is 2 or more when V 2 and between the W 2 respectively with each other are the same But it may be different, O * represents the oxygen atom bonded to an organic radical B. )
[Formula 10]

(In the formula (A-8), R 1 and R 2 represents a hydrogen atom or a methyl group independently, O * represents the oxygen atom bonded to an organic group B.)
[Formula 11]

(formula (a-9) in, n 26 represents an integer of 2 ~ 6, O * represents the oxygen atom bonded to an organic group B.)
[formula 12]

(in the formula (a-10), O * represents an oxygen atom bonded to an organic group B.)
[formula 13]

(in the formula (a-11), n 28 represents an integer of 2 ~ 8, O * represents the oxygen atom bonded to an organic group B .)
[formula 14]

(in the formula (a-12), O * represents the oxygen atom bonded to an organic group B.)
[formula 15]

(in the formula (a-13), n 26 is 2 to 6 represents an integer, O * represents the oxygen atom bonded to an organic group B.)
[Chemical formula 16]

(in the formula (a-14), O * represents the oxygen atom bonded to an organic group B.)
[formula 17 ]

(in the formula (a-15), O * represents the oxygen atom bonded to an organic radical B.
[Formula 18]

(In the formula (A-16), O * represents the oxygen atom bonded to an organic group B.)
[Formula 19]

(In the formula (A-17), * - is bonded to an organic group B represents a terminal.)
[formula 20]

(formula (a-18) in, NH * represents NH group bonded to an organic radical B.)
[Requested item 3]
　The compound represented by the general formula (1) is a laminate of claim 2 wherein the the represented (meth) acrylate by the following general formula (2).
[Formula 21]

(In the formula (2), k represents an integer of from 0 to 3, R 1 ~ R 6 independently represent a hydrogen atom or a methyl group, m 1 and n 1 are independently between 0 and 100 It represents an integer.)
[Requested item 4]
　The water absorbing layer (B) is
　a compound represented by the general formula (1) The laminate according to claim 2 or 3 comprising a crosslinked resin of a polymerizable composition comprising a following inorganic fine diameter 10 [mu] m.
[Requested item 5]
　The hydrophilic layer (A) and the water-absorbing layer (B) and the linear expansion coefficient difference is 0 ~ 300 × 10 of -6 laminate according to any one of claims 1 to 4 in the range of / K.
[Requested item 6]
　The hydrophilic layer (A) and the water-absorbing layer (B) and the linear expansion coefficient difference is 0 ~ 160 × 10 of -6 laminate according to any one of claims 1 to 4 in the range of / K.
[Requested item 7]
　Laminate according to any one of claims 1 to 6 applications is an optical article.
[Requested item 8]
　Wherein the optical article is an optical film, optical disc, optical lenses, spectacle lenses, eyeglasses, sunglasses, contact lenses, goggles, helmet shields, headlamps, laminate according to claim 7 is any one selected from the group consisting of the tail lamp .