WO1999026951A1

WO1999026951A1 - Phosphate/copper compound, composition containing the compound, and application product

Info

Publication number: WO1999026951A1
Application number: PCT/JP1998/005202
Authority: WO
Inventors: Hiroki Katono
Original assignee: Kureha Kagaku Kogyo Kabushiki Kaisha
Priority date: 1997-11-21
Filing date: 1998-11-19
Publication date: 1999-06-03

Abstract

A novel phosphate/copper compound capable of efficiently cutting off light in the near infrared region; and a composition and an application product both containing the compound. The phosphate/copper compound is obtained by reacting a compound represented by the following formula (I): PO(OH)nX3-n with a copper ion donor, wherein X represents (a) or (b) or (wherein X1 represents a monovalent organic group and X2 represents a divalent organic group); and n is 1 or 2.

Description

Description Copper ester phosphate compounds, compositions containing such compounds, and applied products

The present invention relates to a phosphoric acid ester copper compound, a near-infrared absorbing composition containing the compound, and an optically applied product. More specifically, the present invention relates to a novel copper ester phosphate compound, which emits light in the near-infrared region. A composition capable of efficiently and evenly applying a force, an optical filter obtained from the composition (visibility correction filter, noise cut filter, heat ray absorption filter), and a device (plasma) including the optical filter Display device 'Optical fiber device · Camera · CCD camera · CMOS image sensor · Artificial retina · Image input device · Infrared communication environment maintenance device), optical fiber and eyeglass lens. Background technology

Conventionally, as an optical filter (near-infrared cut filter) capable of cutting light in the near-infrared region, a glass optical filter in which copper ions are contained in a special phosphate glass has been used.

However, optical filters made of glass are heavy and have high hygroscopicity, and it is difficult to form, cut, and grind the optical filters.

However, it has many disadvantages.

Therefore, the development of an optical filter that is light, has low hygroscopicity, and is easy to process has been strongly desired.

The near-infrared cut filter must be able to sufficiently transmit light in the visible region and efficiently and uniformly cut (absorb well) the light in the near-infrared region (800-1000 nm). Is desirable.

An optical filter having a variation in light absorption characteristics in the near-infrared region, for example, the light absorptance near 800 nm is extremely larger than the light absorptivity near 100 nm If the optical filter is intended to sufficiently absorb light in the vicinity of 100 nm, light in the visible region is also absorbed by the optical filter, and the transmittance of light in the visible region is reduced. Disclosure of light

[Problems to be solved by the invention]

The present invention has been made based on such circumstances.

A first object of the present invention is to provide a novel phosphoric acid ester copper compound capable of efficiently cutting light in the near infrared region (800 to 100 nm). A second object of the present invention is to efficiently cut light in the near infrared region and to have good dispersibility or solubility in various media. A third object of the present invention is to provide a powdery substance that can be used in the field, which can efficiently cut light in the near-infrared region and disperse or dissolve in various media. Provide a liquid material that has good (compatibility) and can be used in a wide range of fields together with such a medium or alone.

A fourth object of the present invention is to efficiently cut C light in the near-infrared region, have good dispersibility or solubility (compatibility) with various media, and together with such media, or It is to provide a paste-like substance that can be used in a wide range of fields by itself.

A fifth object of the present invention is to provide a composition capable of efficiently cutting light in the near infrared region.

A sixth object of the present invention is to provide a liquid composition that can efficiently cut light in the near infrared region.

A seventh object of the present invention is to provide a cost-effective composition that can efficiently cut light in the near infrared region. An eighth object of the present invention is to provide a polymer composition capable of efficiently and evenly cutting light in the near infrared region.

A ninth object of the present invention is to provide a monomer composition from which the polymer composition can be prepared.

A tenth object of the present invention is to provide a resin composition capable of efficiently and evenly cutting light in a near infrared region.

An eleventh object of the present invention is to provide a resin composition having excellent near-infrared absorption characteristics and visible light transmittance.

A twelfth object of the present invention is to provide a resin composition which is light in weight, has low hygroscopicity, and is easy to apply such as molding, cutting and polishing.

A thirteenth object of the present invention is to provide a coating agent having near infrared absorption characteristics.

A fourteenth object of the present invention is to provide an adhesive having near infrared absorption characteristics.

A fifteenth object of the present invention is to provide a pressure-sensitive adhesive having near-infrared absorption properties.

An i-th object of the present invention is to provide a near-infrared absorbing film capable of efficiently and evenly cutting light in a near-infrared region.

A seventeenth object of the present invention is to provide a near-infrared absorbing plate capable of efficiently and evenly cutting light in a near-infrared region.

An 18th object of the present invention is to provide a near-infrared absorbing member capable of efficiently and evenly cutting light in a near-infrared region.

A nineteenth object of the present invention is to provide an optical filter capable of efficiently and evenly cutting light in a near infrared region.

A 20th object of the present invention is to provide an optical filter (visibility correction filter) having a visibility correction function.

A twenty-first object of the present invention is to provide an optical filter (noise cut filter) having a noise cut function. A second object of the present invention is to provide an optical filter (heat ray absorption filter) having a heat ray absorption function.

A second object of the present invention is to provide a camera comprising an optical filter capable of efficiently and evenly cutting light in a near infrared region as a visibility correction filter for a light receiving element. It is in.

A twenty-fourth object of the present invention is to provide a CCD camera including an optical filter capable of efficiently and evenly cutting light in the near-infrared region as a visibility correction filter for a CCD, and An object of the present invention is to provide an image input device equipped with this. A twenty-fifth object of the present invention is to provide a CMOS image sensor including an optical filter (visibility correction filter) that can efficiently and uniformly cut light in the near infrared region, and An object of the present invention is to provide an image input device equipped with this.

A twenty-sixth object of the present invention is to provide an artificial retina having an optical filter (visibility correction filter) capable of efficiently and evenly cutting light in the near-infrared region, and mounting the artificial retina. To provide an image input device.

A twenty-seventh object of the present invention is to provide an infrared communication environment maintenance device including, as a noise cut filter, an optical filter capable of efficiently and evenly cutting light in a near infrared region. It is in.

A twenty-eighth object of the present invention is to provide a plasma display device in which an optical filter capable of efficiently and uniformly cutting light in a near-infrared region is arranged on the front surface of a panel. .

A twentieth object of the present invention is to provide an optical fiber and an optical fiber device capable of efficiently and evenly cutting light in the near infrared region. A 30th object of the present invention is to provide a spectacle lens that can efficiently and uniformly cut light in the near infrared region and has an effect of suppressing the onset of cataract. A thirty-first object of the present invention is to provide a window material capable of efficiently and evenly cutting light in the near infrared region. [Means for solving the problem]

The phosphoric acid ester copper compound of the present invention is obtained by reacting a compound represented by the following formula (I) with a copper ion supplying compound. o c H

Formula (I): P〇 (OH) _n X,-„

[However, X is

X ¹ — C— 0— X ² — 0— or X ¹ —〇一 C-X ² — 0-li II

0 〇

(X ¹ represents a monovalent organic group, and X ² represents a divalent organic group.)

And n is 1 or 2. Further, the phosphoric acid ester copper compound of the present invention is obtained by reacting a compound represented by the following formula (II) with a copper ion supplying compound.

Formula (Π): P 0 (0 H) R

[However, R is

R ¹ C 1 〇 ^ -R 〇

! ί

0

R '-0 R ² 0 ^ T ~~ or

(R ¹ represents an alkyl group, a phenyl group or an alkenyl group, R ² represents a substituted or unsubstituted alkylene group,

R ³ represents an alkylene group. p and q are integers of 1 to 5, respectively. ) And n is 1 or 2. The near-infrared absorbing powdery substance of the present invention comprises the above-mentioned phosphate copper compound It is characterized by the following.

The near-infrared absorbing liquid substance of the present invention is characterized by comprising the above-mentioned phosphoric acid ester copper compound.

The near-infrared absorbing paste-like substance of the present invention is characterized by comprising the above-mentioned phosphoric acid ester copper compound.

The near-infrared absorbing composition of the present invention is characterized by containing the phosphoric acid ester copper compound.

Further, the composition of the present invention is characterized by being in a liquid state.

Further, the composition of the present invention is characterized by being in a paste form.

Further, the composition of the present invention is characterized by containing a monomer.

Further, the composition of the present invention is characterized by containing a polymer.

The coating agent of the present invention is characterized by comprising the composition of the present invention _:

The adhesive of the present invention is characterized by comprising the composition of the present invention.

The pressure-sensitive adhesive of the present invention is characterized by comprising the composition of the present invention.

The near-infrared absorbing film of the present invention is characterized in that a near-infrared absorbing layer made of the powdery substance of the present invention is formed on the surface of a film substrate.

Further, the near-infrared absorbing film of the present invention is characterized in that a near-infrared absorbing layer made of the liquid substance of the present invention is formed on the surface of a film substrate.

Further, the near-infrared absorbing film of the present invention is characterized in that a near-infrared absorbing layer comprising the pasty substance of the present invention is formed on the surface of a film substrate.

Further, the near-infrared absorbing film of the present invention is characterized by comprising the composition of the present invention.

Further, the near-infrared absorbing film of the present invention is characterized by being obtained by applying the coating agent of the present invention to the surface of a film substrate.

Further, the near-infrared absorbing film of the present invention is characterized by comprising a composite film having an intermediate layer formed from the adhesive of the present invention.

Further, the near-infrared absorbing film of the present invention is characterized by comprising a composite film having an intermediate layer formed from the pressure-sensitive adhesive of the present invention. The near-infrared absorbing plate of the present invention is characterized in that a near-infrared absorbing layer made of the powdery substance of the present invention is formed on the surface of a substrate.

The near-infrared absorbing plate of the present invention is characterized in that a near-infrared absorbing layer made of the liquid substance of the present invention is formed on the surface of a substrate.

The near-infrared absorbing plate of the present invention is characterized in that a near-infrared absorbing layer made of the base material of the present invention is formed on the surface of a substrate.

The near-infrared absorbing plate of the present invention comprises the composition of the present invention.The near-infrared absorbing plate of the present invention is obtained by applying the coating agent of the present invention to the surface of a substrate. It is characterized by.

Further, the near-infrared absorbing plate of the present invention is characterized by comprising a composite plate having an intermediate layer formed from the adhesive of the present invention.

Further, the near-infrared absorbing plate of the present invention is characterized by comprising a composite plate having an intermediate layer formed from the binding agent of the present invention.

The near-infrared absorbing member of the present invention is characterized in that the powdery substance of the present invention is contained in a cell.

The near-infrared absorbing member of the present invention is characterized in that the liquid substance of the present invention is accommodated in a cell.

The near-infrared absorbing member of the present invention is characterized in that the pasty substance of the present invention is accommodated in a cell.

The near-infrared absorbing member of the present invention is characterized in that a liquid composition of the present invention is contained in a cell.

Further, the near-infrared absorbing member of the present invention is characterized in that a paste-shaped composition of the present invention is accommodated in a cell.

The optical filter of the present invention is obtained from the phosphoric acid ester copper compound of the present invention.

The optical filter of the present invention is characterized by being obtained from the composition of the present invention. The visibility correction filter of the present invention is obtained from the composition of the present invention. I do.

The noise cut filter of the present invention is characterized by being obtained from the composition of the present invention.

The heat ray absorbing filter of the present invention is characterized by being obtained from the composition of the present invention.

The optical fiber of the present invention is characterized by being obtained from the composition of the present invention. The spectacle lens of the present invention is characterized by being obtained from the composition of the present invention. The plasma display device of the present invention is characterized in that the optical filter of the present invention is arranged on the front surface of the panel.

The optical fiber device of the present invention is characterized in that the optical filter of the present invention is provided in a lighting part.

The power lens of the present invention is characterized in that the visibility correction filter of the present invention is mounted as a filter for a light receiving element.

The CCD camera of the present invention is characterized in that the visibility correction filter of the present invention is mounted as a filter for CCD.

A CMOS image sensor of the present invention is characterized by including the visibility correction filter of the present invention.

The retinal prosthesis of the present invention is provided with the visibility correction filter of the present invention mounted thereon.

An image input device according to the present invention includes the CCD camera according to the present invention.

An image human input device according to the present invention is characterized in that the CMOS image sensor according to the present invention is mounted.

Further, the image input device of the present invention is characterized in that the artificial retina of the present invention is mounted.

An infrared communication environment maintenance device of the present invention is characterized by including the noise cut filter of the present invention.

The window material of the present invention is characterized by comprising the heat ray absorbing filter of the present invention. Further, the resin composition of the present invention is characterized in that a phosphoric acid group derived from the compound represented by the above formula (I) and a metal ion are contained in a polymer.

Further, the resin composition of the present invention contains a phosphoric acid group derived from the compound represented by the above formula (Π) and a metal ion containing copper ion as a main component in a polymer. This is the feature.

[Action]

[1] A phosphoric acid group derived from the compounds represented by the above formulas (I) to (II) (hereinafter also referred to as “specific phosphoric acid group-containing compound”) and a copper ion supplying compound Bond (coordination bond or ionic bond) with the copper ion supplied from, to form a phosphate copper compound.

The groups (X, R) that form the phosphate bond in the specific phosphate group-containing compound are determined by the spectral properties (light absorption properties) of the formed phosphate copper compound and the dispersibility or dissolution in the medium. Has a positive effect on sex. The oxycarbonyl group in the group (X, R) constituting the phosphate bond has a certain degree of polarity, thereby improving the dispersibility or solubility of the phosphate copper compound in the medium. Is done.

By changing the group (X ′, R ¹ ) linked to the oxycarbonyl group, the properties of the group (X, R) constituting the phosphate bond can be changed. Thus, the light absorption characteristics and the dispersibility or solubility in the medium can be appropriately adjusted.

[2] A phosphate group derived from a specific phosphate group-containing compound binds to a metal ion, whereby the metal ion is contained in the polymer via the phosphate group.

The resin composition, which is a polymer having metal ions held through a phosphate group, exhibits light absorption characteristics characteristic in the near infrared region. Further, since the metal ion and the phosphate group are bonded to form a complex, the metal ion is contained in a state of being uniformly dispersed in the polymer, and the obtained resin composition is Light diffusion is extremely small and good transparency is obtained. ί3] An optical filter comprising a resin composition containing a metal ion via a phosphate group derived from a specific phosphate group-containing compound has a close proximity, as is clear from the results of Examples described later. The light in the infrared region (800 to 100 nm) can be efficiently cut, and the light in the region can be cut evenly (for example, light of 800 nm). The ratio of the light transmittance of 100 nm to the transmittance (T !. · _T8u ) is 2 or less, and the ratio of the absorbance of 100 nm to the light absorption of 800 nm (A , ₀₀₀ Z Α, οο) is 0.5 or more].

[Embodiment of the invention]

Hereinafter, the present invention will be described in detail.

The phosphoric acid ester copper compound of the present invention is a compound obtained by reacting a specific phosphoric acid group-containing compound with a copper ion supplying compound:

Further, the resin composition of the present invention is a composition comprising a polymer containing a phosphate group derived from a specific phosphate group-containing substrate and a metal ion containing copper ions as a main component. It is.

In the present invention, the “phosphoric acid group” means a group represented by Ρ (0Η) „(η is 1 or 2).

Specific compounds containing phosphoric acid groups>

A specific phosphoric acid group-containing compound represented by the above formula (I) [hereinafter, also referred to as “specific compound (1)”] has a phosphoric acid group [PO (OH) 1 And a phosphoric acid diester (when _n = 1) or a phosphoric acid monoester (when n = 2) having at least one oxycarbonyl group (one C 00— or —0 C 0).

In the above formula (I) representing the specific compound (1), X represents a group constituting a phosphate bond.

X ′ in this group (X) represents a monovalent organic group selected from an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a characteristic group containing oxygen, and the like. X ^{2 in} is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an acid It represents a divalent organic group selected from elemental groups containing nitrogen.

Note that the group represented by X ′ may contain a polymerizable unsaturated bond. Further, the groups represented by X ¹ and X ² may include an oxycarbonyl group (—COO— or 10 C 0—.).

The resin composition of the present invention is characterized in that a phosphate group is introduced by a specific phosphate group-containing compound represented by the above formula (II) [hereinafter, also referred to as “specific compound (2)”]. This specific compound (2) has, in its molecular structure, a phosphoric acid group [PO (OH) „—] and at least one oxycarbonyl group (1 C 00— or 1 C 0— ) Or a monoester of phosphoric acid (when n = 2).

In the above formula (II) representing the specific compound (2), R represents a group constituting a phosphate bond.

R in this group (R) is an alkyl group such as a meryl group, an ethyl group, a propyl group, an n-butyl group and an isobutyl group: a vinyl group, an aryl group, a propyl group and an isopropyl group; An alkenyl group (polymerizable group) such as a group; or a phenyl group. In addition, R in the group ^(R): the Echiren group, Bok Li methylene group, Tetoramechire down group, the Kisamechiren group, an alkylene group such as propylene group, these § alkylene group, a substituted a part of hydrogen atoms It may be.

R ³ in the group (R) represents an alkylene group such as an ethylene group. In addition, the number p of repeating alkylene oxide groups (—R ²⁰ —) in the group (R) is preferably 1 to 5, and is preferably Is 3 or more, more preferably 5. If the value of p exceeds 5, the resulting polymer will have a drastically reduced hardness, and will not be practical as an optical filter.

The number of repetitions q of the alkylene oxide group (_R ³⁰ —) in the group (R) is 1 to 5.

Specific examples of the group (R) constituting the phosphate bond include:

Acetyloxyethoxy, acetyloxypropoxy, acetyloxybutoxy, acetyloxypentyloxy, acetyloxyhexyloxy An acetyloxy alkoxy group such as an acetyloxy heptyloxy group, an acetyloxy octyloxy group, an acetyloxydecyloxy group,

Propionyloxyethoxy, propionyloxypropoxy, propionyloxybutoxy, propionyloxypentyloxy, propionyloxyhexyloxy, propionyloxyquinheptyloxy, propionyloxyoctyloxy, propionyloxy A propionyloxyalkoxy group such as a xydecyloxy group,

Petilyloxyetoxy, Petilyloxypropoxy, Butyryloxybutoxy, Petilyloxypentyloxy, Petilyloxyhexyloxy, Petilyloxyheptyloxy, Petilyloxyoctyloxy, Butylyloxy Butylyloxyalkoxy group such as decyloxy group,

'Reli-Roxy-Ethoxy, P'Reli-Roxy-Propoxy, Reli-Roxy-Butoxy, Berelli-Loxy-Benoxy, Berelli-Roxy-Hexyloxy, Valeryl-Roxy-Heptyloxy, P'Rel-Roxy Paryloxy groups such as octyloxy group and reryoxydecyloxy group,

Bivaloyloxyethoxy, Bivaloyloxypropoxy, Bivaloyloxybutoxy, Bivaloyloxypentyloxy, Bivaloyloxyquinoxyloxy, Pipa'royloxyheptyloxy, Vivaloyloxy Bivaloyloxyalkoxy groups such as octyloxy, bivaloyloxydecyloxy, lauroyloxyethoxy, lauroyloxypropoxy, lauroyloxybutoxy, lauroyloxypentyloxy, lauroyl Alkylcarbonyloxyalkoxy groups typified by radihexyloxyalkoxy groups such as quinhexylquinine, lauroylquinheptyloxy, lauroyloxyoctyloxy, and lauroyloxydecyloxy;

Acryloyloxyethoxy, Acryloyloxypropoxy, Acryloyloxybutoxy, Acryloyloxypentyloxy, Acryloyloxyhexyloxy, Acryloyloxyheptyloxy Groups, acryloyloxy, xyoctyloxy, acryloyloxydecyloxy, etc. A xyalkoxy group,

Methacryloyloxyethoxy group, Methacryloyloxypropoxy group, Methacryloyloxybutoxy group, Methacryloyloxypentyloxy group, Methacryloyloxydihexyloxy group, Methoxy group A meta-chloroyloxy alkoxy group such as a crystalloyloxyheptyloxy group, a meta-chloroyloxy octyloxy group, and a methyl chloroyloxydecyloxy group;

2-methacryloyloxy 1-methacryloyloxyalkoxy group having a substituent containing an aromatic ring such as phenoxymethylethoxy group,

Propioloyloxypropoxy group, Propioloyloxypropoxy group, Propioloyloxybutoxy group, Propioloyloxypentyloxy group, Propioloyloxyhexyloxy group, Propioloyloxyquinheptyloxy group Propioloyloxyalkoxy groups such as pioloyloxyoctyloxy group, propioyloxydecyloxy group, etc.

Crotonoxyethoxy, crotonyloxypropoxy, crotonyloxybutoxy, crotonyloxypentyloxy, crotonyloxyquinoxy, crotonyloxy, etc. Crotyloxyalkoxy groups such as butyloxy, crotonoxyloxyoctyloxy, and crotonyloxydecyloxy

An alkenylcarbonyloxyalkoxy group represented by;

Benzoyloxyethoxy, benzoyloxypropoxy, benzoyloxybutoxy, benzoyloxypentyloxy, benzoyloxyhexyloxy, benzoyloxyheptyloxy, benzoyloxyoctyl A benzoyloxyalkoxy group represented by an oxy group, a benzoyloxydecyloxy group, and the like;

Methoxycarbonylethoxy, methoxycarbonylpropoxy, methoxycarbonylbutoxy, methoxycarbonylpentyloxy, methoxycarbonylhexyloxy, ethoxycarbonylethoxy, ethoxycarbonyloxy, ethoxycarbonyl Ethoxycarbonylbutoxy group, ethoxycarbonylpentyloxy C, ethoxycarbonylhexyloxy, propoxycarbonylethoxy, propoxycarbonylpropoxy, propoxycarbonylbutoxy, propoxycarbonylpentyloxy, propoxycarbonylhexyloxy, butoxycarbonylethoxy, butoxycarbonylpropoxy Alkoxycarbonylalkoxy groups such as butoxycarbonylbutoxy, butoxycarboxylpentyloxy, and butoxycarboxyhexyloxy; propenyloxycarbonylethoxy and propenyloxycarbonylpropoxy; , Propenyloxycarbonylbutyne, propenyloxycarbonyl pentyloxy, propenyloxycarbonylhexyloxy, butenyloxy Carbonyloxy, butenyloxycarbonylpropoxy, butenyloxycarbonylbutoxy, butenyloxycarbonylpentyloxy, butenyloxycarbonylhexyloxy, pentynyloxycarbonylethoxy An alkenyloxycarbonylalkoxy group represented by a pentenyloxycarbonylpropoxy group, a pentenyloxycarbonylbutoxy group, a pentenyloxycarbonylpenteneoxy group, a pentenyloxycarbonylhexyloxy group, and the like;

A phenoxycarbonylalkoxy group represented by a phenoxycarbonylethoxy group, a phenoxycarbonylpropoxy group, a phenoxycarbonylbutoxy group, a phenoxycarbonylpentyloxy group, a phenoxycarbonylhexyloxy group;

2—Examples include groups having two oxycarbonyl groups (—C 00— and 10 C—) represented by a methyloxyloxycarbonylpentyloxy group and the like.

Among these, a methacryloyloxyalkoxy group having a substituent containing an aromatic ring and a group having two oxycarbonyl groups are preferable.

Here, specific examples of the specific phosphoric acid group-containing compound include (phosphonooxy) monoacetic acid methyl ester, (phosphonooxy) -acetic acid 1-ethyl ester, and (phosphonooxy). Monoacetic acid 1— (2— (phospho-nonoxy) ethyl) Ter, (phosphonoxy) monoacetic acid 1-propyl ester, (phosphonoxy) monoacetic acid 1-1 (3— (phosphonoxy) propyl) ester, (phosphonoxy) monoacetic acid 1-butyl ester, (phosphonoxy) one Acetic acid 1 — (4- (phosphonoxy) butyl) ester, (phosphonoxy) monoacetic acid 1 —pentyl ester, (phosphonoxy) monoacetic acid 1- (5 — (phosphonoxy :) pentyl) Ester;

Methoxycarbonylethyl phosphate, bis (methoxycarbonylethyl) phosphate, ethoxycarbonylethyl phosphate, bis (ethoxycarbonylethyl) phosphate 2 — (pentyl cosiloxy) 3 — (phosphonooxy) methyl monopropanoate, 2, 3 — bis (phosphonoquinine) methyl propanoate, 3 — clo 2 — (phosphonooxy) methyl propanoate, 2 — (phosphonooxy) Methyl monobutyrate, 3,3,3—Trifluoro-2— (phosphoquinoline) methyl propanoate, 3—Fluoro-2— (phosphooxy) Propanoic acid methyl ester, 3— (Phosphoronoxy) ) —Probanic acid 1-methylethenyl ester, 2, 3 —Bis (phospho-nonoxy)- Peptic acid 1-butyl ester, 2— (phosphonooxy) monopropanoic acid 1-year-old octyl ester, 2— (phospho nonoxy) monopropanoic acid 1—decylester, 2— (phosphoonoxy) monopropanoic acid 1-dodecyl ester; methoxycarbonylpropyl phosphate, bis (methoxycarbonylpropyl) phosphate, ethoxycarbonylpropyl phosphate, bis (ethoxycarbonylpropyl) phosphate, 3 — ( Phosphonoxy) monobutyric acid 1 monodecyl ester, 3 — ('phosphonooxy) monobutyric acid 1-dodecyl ester:

Methoxycarbonylbutyl phosphate, bis (methoxycarbonylbutyl) phosphate

6- (Phosphonoxy) monohexanoic acid 1 — (2 — ((1 —oxo 1 2 —propenyl) oxy) ethyl) ester, 6 — (phosphonooxy) monohexanoic acid 1 — (2 — ( (2 -Methyl-1 -oxo-1 2 -propenyl) oxy) ethyl) ester, 6-(phosphonooxy) 1-hexanoic acid 1 — (4 1 (: (1 -oxo 1 2 —Prodoxy) oxy) butyl) ester, 6 — (phosphonoxy.) 1-hexanoic acid 1 — ('6 — (2-((2 —Methyl-1 —oxo— 2 —Propenyl)) (Oxy) ethoxy) _ 6 -oxohexyl) ester, 2 — ('phosphonooxy) -hexanoic acid 1 monodecyl ester:

7- (2—Methoxy-3— (phosphonooxy) propoxy) monoheptanoic acid (phenylmethyl) ester;

2 — (phosphonooxy) monooctanoic acid 1 — decyl ester;

2 — (phosphonooxy) 1 2 — propenoic acid 1 (2 — hydroxyxethyl) ester, 2 — (phosphooxy) 1 2 — propenoic acid 1 — ethyl ester,

2 — (Phosphonomethyl.) 1 3 — (Phosphonooxy) 1 2 —Propenoic acid 1-methyl ester, 3 — (3—Methoxyl 4 — (Phosphonooxy) phenyl) — 2 —Propenoic acid 1 Methyl ester, 2-bromo-1- (dichlorophenyl) -13- (phospho-nonoxy) 2-propenoic acid 1-ethyl ester, 2-chloro-1-(phospho-nonoxy) 1-3- (trichloromouth phenyl) 1) 2-Proponic acid 1-Ethyl ester, 2-Bromo 3— (Cross phenyl) 3— (Phosphonoxy) 1-2—Propenoic acid 1—Ethyl ester, 2-Bromo-13— (Phosphonoxy) 1-3 — (Trichlorophenyl) 1 2 —Propenoic acid 1 —Ethylester, 2 —Chloro-3 — (Dichloromouth phenyl) 1 3 — (Phosphorooxy) 1 2 —Propenoic acid 1 —Ethyl ester, 2 —Chloro-3 — (Chlorophenyl)

3 — (phosphonooxy) — 2 —propenoic acid 1 —ethyl ester;

3 — (phosphonoxy) 1 2 —butenoic acid 1 —ethyl ester;

2 — (phosphonoquinone) — benzoic acid, 2 — (phosphonooxy) monobenzoic acid 1 — methyl ester, 3 — (phosphonooxy) monobenzoic acid 1 — methylester, 4 1 (phosphonooxy) Benzoic acid 1-methyl ester, 4- (phosphonooxy) monobenzoic acid 1-ethyl ester, 2— (phosphonooxy) —benzoic acid 1— (: 1-methylethyl) ester, 2— (phosphonooxy) —benzoic acid Acid 1- (2-methylpropyl) ester, 4- (phosphonooxy) monobenzoic acid 1-butyl ester, 4— (phospho-onoxy) -benzoic acid 4 1- (2-Methyl-1-oxo-1-2-propoxynyl) oxy) butyl) Ester 4 1- (phosphono) oxybenzoic acid 1 1-hexyl ester, 2— (phospho-nonoxy) monobenzoate Acid 1- (2-carboxyphenyl) ester, 4-((phosphono) oxy) -benzoic acid 1- (2-ethylhexyl) ester, 4-((phospho-nonoxy) -benzoic acid 1-heptyl ester, 2— ( Phosphonoxy) —Benzoic acid 1-year-old octyl ester, 4- (phosphonooxy) —Benzoic acid nonyl ester, 4- (phosphonooxy) —Benzoic acid decyl ester, 2 -— (phosphonooxy.) Monobenzoic acid 1— Decyl ester;

Hydroxyacetic acid 1 formyl 1 2 — (phosphonooxy) ethyl ester, chloroacetic acid 2 — (phosphonooxy) 1 1.3 — propanediyl ester, kuguchiacetic acid 3 — hydroxy 1-2 2 — ( Phosphonoxy) propyl ester, dik Mouth acetic acid 3 —hydroxy-2 — (phosphonoxy) propyl ester;

3 — (Ethylthio) —pronic acid 2 — (phospho-onoxy) ethyl ester 3 — ((2,3—dioxypropyl) 1000) miponic acid 2 — (phosphonoxy) ethyl ester, 3 — mercapto Propanoic acid 2 — (phosphonoxy) ethyle ester, 3 — methylcaptopropanoic acid 1 — methyl 1 2 — (1 — methyl 2 — (phosphonoxy) ethoxy) ethyle ester, 2 — methyl phosphinate nicobis (oxymethylene) Ester, 2-methylpropanoic acid 2- (phosphonooxy) ethyl ester, 2,2-dimethylphosphonicobis (oxymethylene) ester, 22-Dimethylpropanoic acid (phosphonooxy) methyl ester, 22-dimethylpropane Acid phosphini nico bis (Oxy 9 Nanjiiru) ester;

Butanoic acid 1-((phospho-onoxy) methyl) 1 1 2—Ethylene diester, Butanoic acid 1— (2— (Phosphoro-onoxy) ethyl) 1,2—Ethenyl ester, butanoic acid 3,5—Bis (Phosphonoxy) cyclohexyl ester, butyric acid 5,5—difluoro-1-4-oxo-1 — ('(phosphonooxy) methyl) heptyl ester, butanoic acid 4-oxo-1 2 — ((phosphonooxy) Methyl) nonadecyl ester, 2 — methylenebutanoic acid 7 — black 6 — ( Phosphonooxy) heptyl ester, 2,3-dimethyl-2-((1-methylethyl) phosphinico bisbutanoate (oxy 6, 1, 1-hexanediyl) ester;

Hexanoic acid 1 — ((phospho nonoxy) methyl) 1,1,2 — ethane diester, phosphinicobis hexanoate (oxy 1,3,1,2 — puntolyl) ester, hexanoic acid 3 — (Phosphonooxy) 1-1,2-cyclopentanedyl ester, hexanoic acid 12 2 — (phosphonooxy) dodecyl ester 2-ethylhexanoic acid phosphine nicobis (oxy 1-12,1—dodecandyl) ester:

Heptanoic acid 1 — ((phosphonooxy) methyl) 1-1,2—Ethandiyl ester, 3, 6—Dimethylheptanoic acid 1.1 ((phosphonooxy) methyl) 1-1.2.

Octanoic acid 1 — ((phospho-onoxy) methyl) 1 1, 2 — ethanedilyster, octanoic acid 3 — ((2 — methyl 1 1oxo 1 2 — bronilyl) oxy) 1 2 — (phospho-onoxy) propyl ester, octanoic acid 2 — Hydroxy-3- 3- (phospho-onoxy) propyl ester, octanoic acid 2 — (phospho-onoxy) phenyl ester, octanoic acid 5,5 —Difluoro-4-oxo-one 2 — ((phospho-onoxy) methyl) undecyl ester, 7 —methyl-3 —oxo-octanoic acid 2 —oxo-one 3 — (phospho-onoxy) propyl ester, 3, 7 —dimethyl Octanoic acid ((phosphonooxy) methyl) 1,1,2-diene benzyl ester;

Phosphinicobis dodecanoate (Oxy-3, 1.2-propanetriyl) ester:

Hexadecanoic acid phosphinicobis (oxy (2-hydroxy-3,1-propyl)) ester, hexadecanoic acid phosphinicobis (oxy3,1,2-propanetrilyl) ester, hexadecane Phosphinicobis (oxy-1,3-, propanediyl) ester, phosphine nicobis (oxy-1,3,1,2-propanetriyl) ester, hexadenic acid Phosphinicobis (oxy-2- (ethynyl-1-ylidene)) decanoate, hexadenic acid Phosphinicobis (oxy (2—hydroxy-1,3,1-prono, benzyl)) ester, hexadeca Phosphinicobis (oxy-1,3,1,2-propanthyl-1-14C) ester;

Phosphonicobis decanoic acid (oxy (2,2-dimethyl-3.1-p-panzyl)) ester, phosphinicobis decanoic acid (oxy-3,1,2—propane triyl) ester, o Phosphine nicobis (oxy-1,3,1-propanezyl) ester

Tetradecanoic acid phosphinicobis (oxy-3,1,2—propanetriyl) ester:

2-Propenoic acid (phosphonooxy) methyl ester, 2-Propenoic acid (4-((phosphonooxy) methyl) cyclohexyl) methyl ester, 2-Phosphoric acid nicobis (oxy) -2- (phenoxy (2), 1-E-N-Ziyl)) Ester, 2-Phosphonicobis propenoate (Oxy 2, 1, 1-E-N-Zyl) E-N-Zi-yl, 2-Propenoic acid 2 — (4 — ( Phosphonoxy) ethoxy) phenoxy) ethyl ester, 2—propenoic acid 2— (phosphonooxy) ethyl ester, and 3 — ('(2—ethylhexyl) oxy) 1-1,2—Monoester with propanediol, 2 —Propenoic acid 2 — (3-(2 —

(Phosphonoxy) ethoxy) phenoxy) ethyl ester, 2 — propenoic acid 2 — (2 — (phosphonooxy) ethoxy) ethyl ester, 2 — methyl propenoate 2 — (phosphonoxy) ethyl ester, 2 — propenoic acid Sphinicobis (oxy (2-methyl-2,1 ethanedyl)) ester, 2 — propenoic acid phosphinicobis (oxy (2 — (chloromethyl) 1-2,1 — ethanedyl) ester, 2-propene Acid 1 — (chloromethyl) 1 2 — (phosphonooxy) ethyl ester, 2 — propenoic acid 3 — chloro-1- 2 — ('phosphonooxy) propyl ester, 2 — propenoic acid 2 — (phosphonooxy) 1 3 —

(Tridecyloxy) propyl ester, 2-propenoic acid 3-phenoxy- 1 2 —

(Phosphonoxy) propyl ester, 2-propenoic acid 3 — (4-(3 — (: Phosphonooxy) propoxy) phenoxy) propyl ester, 2-propenoic acid 3 — (3-(3 — (phosphonooxy) propoxy) phenoxy) propyl ester, 2- phosphinicobis propoxylate (oxyxy 3,1 2-propanoic acid) ester, 2-propenoic acid 3 — (dodecyloxy) 1 2 — (phosphonoxy) propyl ester, 2 — propenoic acid 3 — hydroxy 2 — (phosphonoxy) propyl ester, 2 — propenoic acid 2 — (((1 —oxo- 1 2 —propionyl) o) methyl) 1 2 — ((phosphonoquine) methyl) 1, 3-propanediyl ester, 2 —phosphinicobis propoxylate (oxy 4.1 Butyl ester, 2-propenoic acid 4 — (3- (4— (phospho-nonoxy) butane) B) phenoxy) butyl ester, 2—propenoic acid 4- (4- (4-1- (phosphono) oxy) butoxy) phenoxy) butyl ester, 2—propenoic acid 4—chloro-3— (phospho-onoxy) butyl ester, 2— Propenoic acid sphinenicobis (oxy 6, 1-hexanediyl) ester, 2-propenoic acid 12 2-(phospho-onoxy) dodecyl ester, 2-methyl-2-propenoic acid (phospho-nonoxy) methyl ester, 2-methyl-2 —Propenoic acid (4-((phosphonooxy) methyl) phenyl) methyl ester, 2-methyl-2-propenoic acid (4 — ('(phosphonooxy) methyl) cyclohexyl) methyl ester, 2-methyl-2- Propenoic acid 2 — Black mouth 2 — (phosphonooxy) Ter, 2-methyl-2-phosphonicobis propenoic acid (oxy-2,1,1-ethanediyl) ester, 2-methyl-2-phosphonicobis propenoic acid (oxy (2-chloro-2,1 ethanediyl)) ester, 2 —Methyl-2 —propenoic acid 2 — ('4 — (2 — (phosphonoxoxy) ethoxy) phenoxy) ethyl ester, 2 —methyl-1 2 —propenoic acid 2 — (4-(2 — (phosphonooxy) ethoxy) 1 2- (2- (phospho-onoxy) ethoxy) ethyl ester, 2-methyl-2- (propynyl) -2-ethylpropenoic acid 2- (3-phosphonoxy) ) Ethoxy) phenoxy) ethyl ester, 2-methyl-2-propenoic acid 2 — ((phosphonooxy) phenyl ) Echiruesuteru, 2 - methyl - 2-propenoic acid 2 - Black port - 1 i (off Osph-nooxy) ethyl ester, 2-methyl-2-propenoic acid phosphinico bis (oxy (1-1 (chloromethyl) 1-2,2—ethanediyl)) ester, 2-methyl-2-propenoic acid 1—methyl-1-2— (Phosphonooxy) ethylester, 2-methyl-2-propenoic acid phosphinicobis (oxy (2- (chloromethyl) -1,2,1-ethanediyl)) ester, 2-methyl-2-propenoic acid, (( 1,2-Diphenyl ester, 2-methyl-2-propenoic acid methyl-2-((phosphonoxy) ethyl ester, 2-methyl-2-phospho nicobis (2-oxymethyl) 2-propenoate , 1-phenyl)) Ester, 2-Methyl-2-phosphine Nicobis (oxy (1-) 1,2-methyl-2-propenoic acid 1) -Methyl-1-propenylate 1- (phosphonooxy) ethyl ester, 2-methyl-2-propenoic acid 1- (chloromethyl) 1-2- (Phosphonoxy) ethyl ester, 2-methyl-2-propenoic acid phosphinicobis (oxy (methyl-1,2,1-ethanedyl)) ester, 2-methyl-1-probenoic acid 2 — (Phosphonoxy) 1-1 1 1-((phosphonoxy) methyl) ethyl ester, 2-methyl-2-propenoic acid (1—methylethylidene) bis (4,1 phenylenoxy) (1-11 (phosphonoxy) 1-2,1—ethanediyl) ) Ester, 2-methyl-2-propenoic acid 2 — Phenyl 2 — (phosphooxy) ethyl ester, 2-methyl-2-propanoic acid Osfinicobis (oxy-3, 1-propanediyl) ester, 2-methyl-2-propenoic acid Phosphinicobis (oxy (2—hydroxy-3, 1—prono, ndiyl)) ester, 2-methyl-1-propene 2,3-bis ('phosphonoxy) propyl ester, 2-methyl-2-propenoic acid 2- (phosphonoxy) 1-1,3-propanediyl ester, 2-methyl-1-propenoic acid 3-chloro-2- ( Phosphonoxy) propyl ester, 2-methyl-2-propenoic acid 3 — (4- (3- (phosphonooxy) propoxy) phenoxy) propyl ester, 2 —methyl-2-propenoic acid 2 — Hydroxy-1 3 — (Phosphonoxy) .) Propyl ester, 2-methyl_2-propenoic acid 3 — (phosphonoxy) propyl ester , 2-Methyl monopropenoic acid , 1, 3 — propanetrilyl) ester, 2 — methyl-2-propenoic acid 3 — hydroxy 2 — (phosphonooxy) propyl ester, 2 — methyl monopropenoic acid 3 — (3 — (3-( Phosphonoxy) propoxy) phenoxy) propyl ester, 2-methyl-2-propenoic acid 3 — ((4 — (2 — (phosphononoxy) ethoxy) -12-butynyl) oxy) propyl ester, 2-methyl-2-propenoic acid phosphite Nico bis (oxy (2-1,3-propanezyl)) ester, 2-methyl-1 -propenoic acid 3-phenoxy-2-(phosphonooxy) propyl ester, 2-methyl-2-propenoic acid 3-(benzoyloxy) 1) 2- (phosphonooxy) propyl ester, 2-methyl-1-propenoic acid 3-((5-methyl Heptyl) oxy) 1 2 — (phosphooxy) propyl ester, 2-methyl-2-propenoic acid 2 — (((2 —methyl-1 —oxo-1 2 —probenyl) oxy) 1 2 — (Phosphooxy) methyl) 1, 3 — brondiyl ester, 2 — methyl-2-probenoic acid 2 — ((. (2 —methyl 1 —oxo-1 2 —probenyl) oxy) Methyl) 1-2-((phosphonooxy) methyl) 1-1, 3-propanediyl ester, 2-methyl-12-probenoic acid ((1 -methylethylidene) bis (4, 1-phenyleneoxy)-2-(phosphonooxy) 1,3,1 propanediyl)) ester, 2-methyl-2-propenoic acid 2—ethyl 2- (methyl (phospho-onoxy) methyl) 1,1,3-propanediyl ester, 2-methyl-2-propyl Phosphinicobis (oxy 4,1, butanediyl) ester), 2-Methyl-2-propenoic acid 4 — (3 — (4 — (phosphonooxy) butoxy) Butoxy) butyl ester, 2-Methyl-2-propenoic acid 4 — (4- (4- (phosphonoxy) butoxy) phenoxy :) butyl ester, 2-methyl-2-propenoic acid 1-methyl_3 — (phosphonooxy) butyl ester, 2-methyl-1-propenoic acid 3 —Methyl-5- (phosphonooxy) pentyl ester, 2-Methyl-1-propenoic acid 1—Methyl-14- (phosphonooxy) pentyl ester, 2-Methyl-2-propenoic acid 2—Methyl-2— (phosphonooxy) methyl) Pentyl ester, 2-methyl-2-propenoic acid phosphinicobis (oxyxy 6.1 — Kisanjiiru) ester, 2 - main Chiru 2 Purobe Phosphinicobis (oxy-1,2,1-phenylene) ester, 2-methyl-12-propenoic acid 4- (phosphonooxy) phenyl ester, 2-methyl-2-propenoic acid 2-ethylethyl-3— (phosphonoquinine) Hexyl ester, 2 —methyl-2-propenoic acid 4 — (1 —methyl-1 — (4-(phosphonoxy) phenyl) ethyl) phenyl ester, 2-methyl-2-propenoic acid 4-(phosphonoxy) 1), 7-Heptanediyl ester, 2—Methyl-2-propenoic acid 101-((Hydroxyphenoxyphosphinyl) quinine) 191- (Phosphonoxy) decyl ester, 2-Methyl-2-propenoic acid phosphine Nicobis (oxy-10,1-decandyl) ester, 2-methyl-2-propenoic acid 2 — ('Phosphonoki ) Decyl ester, 2-methyl-2-propenoic acid 1 0.10 —Bis- (phosphonooxy) decyl ester, 2-methyl-2-propenoic acid 1 1 1- (phosphonooxy) pentadecyl ester, 2-methyl- 2-propenoic acid 1 2 — (phospho-onoxy) dodecyl ester, 2-methyl-2-probenoic acid 2,4,6,8,10 —pentamethyl-1- 12 — (phospho-onoxy) tridecyl ester, 2 —Methyl-2-fluorobenzoic acid 20 — (phosphonooxy) eicosyl ester, 2 —Methyl-2-propenoic acid phosphinicobis (oxy — 20, 1 —Eicosanzyl) ester, 2 —Methyl-12-propenoic acid 4 0 — (phosphonoxy) tetracontyl ester, 3 — 4 — (methoxyphenyl)-2 — propenoic acid 2-(phosphonoxy) ethyl Stele, 3— (4— (dodecyoxy) phenyl) 1 2—propenoic acid 2— (phosphothioquinone) 1 1,3—propanezylester, 3— (4— (hexadecitic pheasant) Phenyl) 1 2 —Propenoic acid 2 — (Fosphenoxy) 1 1.3-Propandyl ester, 3 — (4 1 (Methoxyphenyl) 1 2 —Propenoic acid 2 — (Phosphonoxy) 1 1 , 3—Propandyl ester, 3 — (4 — (octyoxy) phenyl) — 2 _propenoic acid 2 — (phosphonoxy) 1, 1, 3 —propanedyl ester, 3 — (4 — methoxyphenyl) _ 2 —Propenoic acid 4- (phosphonoxy) butyl ester, 3— (4-Methoxyphenyl) 1-2—Propenoic acid 6— (Phosphonooxy.) Hexylester, 3— (4-hydroxyl) Phenyl) 1 2 — phosphinic propenoate Cobis (oxy 6, 1 — hexanediyl) ester, 3 — (4-1 (3-butoxy 3-oxo-1-1-propenyl) phenyl) 1 2-phosphinico bis-propenoate (oxy 6, 1-hexanediyl) ) Esters, 3 — (4 — (octyloxy) phenyl) 1-2 — phosphinicobis (propoxy- 10, 1 — decanediyl) ester,

3 — (4 — methoxyphenyl) 1 2 — phosphinicobispropenoate (oxy-10, 1 — decandyl) ester, 3 — (4-methoxyphenyl) 1 2 — pulponic acid 1 2 — ( 'Phosphonooxy) dodecyl ester;

3—Phosphinicobis butenoic acid (oxy-1,9,1—nonanzyl) ester Hep decanofluorophosphinonico bis (oxyxyl 2,1,1 nonyl) ester:

Octadedecenoic acid (Z) —phosphinico bis (oxy (1 — (((1—oxooxodecyl) oxy) methyl) 1-2,1—ethanediyl)) ester,

Octadedecenoic acid (Z) -phospho nicobis (oxy (2-hydroxy 3, 1-propanezyl)) ester:

2,4—Ocephalic nicotinic acid phosphine nicobis ester (Oxy 8, 1—Octane diyl) ester:

4-Methoxy-benzoic acid 2 — ((2-Methyl-1 —oxo-2 —Provenyl) oxy) 1 1 1 (phosphonooxy) ethyl ester, 4 1 ((— 2 —methyl 1 1 —oxo1 2—Propenyl) oxy) —Benzoic acid 2— (Phosphorooxy) ethyl ester, 4-Hydroxy—benzoic acid 2—Hydroxy-1 3— (Phosphoxyonoxy) propyl ester, 2—Hydroxy monobenzoate Acid 2—Hydroxy 3— ⁽ : phosphonoxy) propyl ester, 4 —Methoxybenzoic acid 3 — ((2 —Methyl-1-oxo-1 2 —Propenyl) oxy) 1 2 — (Phosphonoxy) Propyl ester, 3—Hydroxy monobenzoic acid 2—Hydroxy 3— (phosphoonoxy) propyl ester, 4—C (2—Methyl 1—1oxo 1 2— B Bae yl) Okishi) - benzoic acid 1 2 - (Fosufuo Nookishi) dodecyl ester Bicyclo (2.2.1) heptto 5-1-2-carboxylic acid phosphinicobis (oxy2, 1-ethanediyl) ester;

Chloro-4-cyclohexane-l, 2-dicarboxylic acid phosphinicobis (oxo 2.1,3-propanetriol) ester;

Vinclo (2.2.1) heptoto-5-ene1-2-carboxylic acid phosphinicobis (oxy-6,1-hexanediyl) ester. Further, the compounds shown in the following (ii) to (iv) have a simple structure and are preferred from the viewpoint of handling and production.

(i) Alkenylcarbonyloxyalkyl group-containing compound:

Acryloyloxyshethyl phosphate, bis (acryloyloxyshetyl) phosphate, acryloyloxypropyl phosphate, bis (acryloyloxypropyl) phosphate Acryloyloxybutyl phosphate, bis (acryloyloxybutyl) phosphate, acryloyloxybenzyl phosphate, bis (acryloyloxypentyl) phosphate, Acryloyloxyhexyl phosphate, bis (acryloyloxyhexyl) phosphate, acryloyloxyheptyl phosphate, bis (acryloyloxyheptyl) phosphate, phosphoric acid Acryloyloxyoctyl, bisphosphate (acryloyloxyoctyl), acryloyloxydecyl phosphate, bis (acryloyloxydecyl) phosphate, etc. Phosphoric acid ( Bis) acryloyloxylalkyl; methacryloyloxyshethyl, bisphosphonate (methacryloyloxyshethyl), methacryloyloxypropyl phosphate, bisphosphonate (bis) Methacryloyloxypropyl), methacryloyloxybutyl phosphate, bis (methacryloyloxybutyl) phosphate, methacryloyloxypentyl phosphate, bis (methacryloyl) phosphate Oxypentyl), methacryloyloxyhexyl phosphate, bisphosphate

(Methacryloyloxyhexyl), methacryloyloxyquin heptyl, bis phosphite (methacryloyloxyquin heptyl), methacryloyloxy octyl, bis phosphite (bis methacrylate) Liloyloxyoctyl), methacryloyloxydecyl phosphate, bis (methacryloyloxydecyl.), Methacryloyl phosphate Propiooloyl phosphate; bis (phosphoryl) methyl phosphate such as oxy (1-chloromethyl) ethyl and bis (methacryloyloxy (1-chloromethyl) ethyl) phosphate Oxyshetyl, bis (propioyloxyxethyl) phosphate, propylioyloxypropyl phosphate, bis (propioyloxypropyl) phosphate, propiooloyl phosphate Xyloxybutyl, bis (propioyloxypentyl) phosphate, propioyloxypentyl phosphate, bis (propioyloxypentyl) phosphate, propioyloxyhexyl phosphate, bis (phosphate) (Propioyloxyhexyl), propioyloxyheptyl phosphate, bis (propioyloxyheptyl) phosphate, prophosphate (Bis) propioyloxyalkyl phosphates such as pioloyloxyoctyl, bis (propioyloxyoctyl) phosphate, propioloyloxydecyl phosphate, bis (propioloyloxydecyl) phosphate, etc .:

Crotonyloxysheptyl phosphate, bisphosphonate (crotonyloxysheptyl), crotanoyloxypropyl phosphine, bisphosphate (crotonyloxypropyl), crotonoyloxypropyl, phosphate Bis (crotonyloxybutyl) phosphate, crotonyloxypentyl phosphate, bis (crotonyloxypentyl) phosphate, crotonyloxyhexyl phosphate, bis (phosphonyloxyhexyl) phosphate Yloxyhexyl), crotonyloxyheptyl phosphate, bis (phosphonyloxyheptyl) phosphate, crotonyloxyoctyl phosphate, bis (chlorotonyloxy) phosphate Phosphoric acid such as octyl), crotonyloxydecyl phosphate, and bis (phosphonyl quindecyl) phosphate Bis) Black Bok Bruno I Ruo carboxyalkyl.

(ii) Alkylcarbonyloxyalkyl group-containing compound:

Acetyloxyshethyl phosphate, bis (acetyloxyshethyl) phosphate, acetyloxypropyl phosphate, bis (acetyloxypropyl) phosphate, acetyloxybutyl phosphate Bis (acetyloxybutyl) phosphate, acetyloxypentyl phosphate, bis (acetyloxypentyl) phosphate, acetyloxyhexyl phosphate, bis (acetyloxyhexyl) phosphate, phosphorus Acetyloxyheptyl, bis (acetyloxyheptyl) phosphate, acetyloxyoctyl phosphate, (Bis) acetyloxyalkyl phosphates such as bis (acetyloxydecyl) phosphate, acetyloxydecyl phosphate, bis (acetyloxydecyl) phosphate; Propionyloxyshethyl, bis (propionyloxyshethyl) phosphate, propionyloxypropyl phosphate, bis (propionyloxypropyl) phosphate, propionyloxybutyl phosphate, phosphoric acid Bis (propionyloxybutyl), propionyloxypentyl phosphate, bis (propionyloxypentyl) phosphate, propionyloxyhexyl phosphate, bis (propionyloxyhexyl) phosphate , Propionyloxyheptyl phosphate, bis (propionyloxyheptyl) phosphate, propionyloxyoctyl phosphate, Bis (propionyloxydecyl) phosphate, propionyloxydecyl phosphate, bis (propionyloxydecyl) phosphate, etc. (bis) propionyloxyalkyl phosphate; petityloxyshethyl phosphate , Bis (butylyloxyshethyl) phosphate, petyyloxypropyl phosphate, bis (butylyloxypropyl) phosphate, butyloxy butyl phosphate, bis (butylyloxybutyl) phosphate, butylyloxypentyl phosphate, linoleic acid Bis (petityloxypentyl) phosphate, petityloxyhexyl phosphate, bis (petityloxyhexyl) phosphate, petityloxyheptyl phosphate, bis (petityloxyheptyl) phosphate, petityloxyoctyl phosphate, Bisphosphate ), Bis (butylyloxydecyl) phosphate, bis (butylyloxydecyl) phosphate, etc .; valeryl oxochetyl phosphate, bis (valeryl oxethyl) valerate, valeryloxypropyl phosphate To bis (valeryloxypropyl) phosphate, valeryl oxyptyl phosphate, bis (valeryloxybutyl) phosphate, valeryl oxypentyl phosphate, bis (valeryl oxypentyl) phosphate, valeryl oxypentyl phosphate Xyl, bis (valeryloxyhexyl) phosphate, valeryloxyheptyl phosphate, bis (valeryloxyheptyl) phosphate, valeryloxyoctyl phosphate, bis (valeryloxyoctyl) phosphate, valeryl oxyphosphate Roxydecyl, phosphoric acid Scan (Valeri Ruokishideshiru)-phosphate such as (bis) Valeri Ruokishiarukiru; Li Nsan Viva Roy Ruo key shell chill, Li Nsan bis (Viva Roy Ruo key shell chill), Li Pivaloyloxypropyl phosphate, bis (bivaloyloxypropyl) phosphate, piperoyloxybutyl phosphate, bis (bivaloyloxybutyl) phosphate, bivaloyloxypentyl phosphate, Bis (piparyloxypentyl) phosphate, piper'royloxyhexyl phosphate, bis (bivaloyloxyhexyl) phosphate, bivaloyloxyheptyl phosphate, bis (bivaloylquineptyl) phosphate, Phosphoric acid (bis) such as bivaloyoxyctyl phosphate, bis (bivaloyloxyoctyl) phosphate, bivaloyloxydecyl phosphate, and bis (piparyloxydecyl) phosphate ) Bivaloyloxyalkyl;

Lauroyloxyshethyl phosphate, bis (lauroyloxyshethyl) phosphate, lauroyloxypropyl phosphate, bis (lauroyloxypropyl) phosphate, lauroyloxybutyl phosphate, phosphorus Bis (lauroyloxybutyl) phosphate, lauroyloxypentyl phosphate, bis (lauroyloxypentyl) phosphate, lauroyloxyhexyl phosphate, bis (lauroyloxyhexyl) phosphate, Lauroyloxyheptyl phosphate, bis (lauroyloxydiheptyl) phosphate, lauroyloxyoctyl phosphate, bis (lauroyloxyoctyl) phosphate, lauroyloxydecyl phosphate, phosphorus (Bis) lauroyloxyalkyl phosphates such as bis (lauroyloxydecyl acid).

(iii) Benzoyloxyalkyl group-containing compound:

Benzolyoxetyl phosphate, bis (benzoyloxethyl) phosphate, benzoyloxypropyl phosphate, bis (benzoyloxypropyl) phosphate, benzoyl phosphate Bis (benzoyloxypentyl) phosphate, benzoyloxypentyl phosphate, bis (benzoyloxypentyl) phosphate, benzoyloxyhexyl phosphate, bis (phosphate) Benzooxyhexyl) Benzoyloxyheptyl phosphate, Bis (benoxyheptyl) phosphate Benzoyloxyoctyl phosphate, Bis (benoxyoctyl) phosphate Benzoyloxydecyl phosphate, Li (Bis) benzoyloxyalkyl phosphates such as bis (benoxydecyl) phosphate.

(iv) Other compounds: Compounds containing two ester groups, such as phosphoric acid 2—methacryloyloxytoquincarbonylpentyl and bis (2-methacryloyloxytoquinol pentylpentyl);

Compounds having a phenyl group, such as phosphoric acid 2 —methacryloyloxy 1-phenoxymethyl tylethyl, bis (2—methyl chloroyloxy 1 1 —phenoxymethyl tylethyl).

The specific phosphoric acid group-containing compound exemplified above is used alone or in combination of two or more kinds in the reaction with the copper ion supplying compound (the reaction for producing the phosphoric acid ester copper compound of the present invention). be able to.

Examples of the copper ion-supplying compound to be subjected to the reaction with the specific phosphoric acid group-containing compound to obtain the phosphoric acid ester copper compound of the present invention include, for example, copper formate, copper citrate, copper propionate, butyric acid Copper, copper valerate, copper hexanoate, copper heptanoate, copper octanoate, copper nonanoate, copper decanoate, copper decanoate, copper laurate, copper myristate, valmitin Copper alkylcarboxylates having 1 to 18 carbon atoms, such as copper acid and copper stearate; chlorinated, brominated, and fluorinated alkylcarboxylic acids; copper toluate, copper hydroxybenzoate, and the like; Copper cetylsalicylate, copper nitrobenzoate; copper benzoate, copper phenyl phenylate, copper cinnamate, copper dihydroxy cinnamate, bromide of copper benzoate, chlorinated copper benzoate, copper benzoate Aroma such as fluoride Copper salts containing a group; Copper carboxylate having a naphthylene ring such as copper naphthyl acetate, copper naphthylene dicarboxylate, and copper naphthylene dicarboxylate: anhydrides and hydrates of these compounds; examples of copper hydroxide can do.

Of these, copper carboxylate having an aromatic ring, and anhydrides and hydrates thereof are preferable in the case of crystal precipitation.

Further, copper compounds such as copper chloride, copper fluoride, copper nitrate, copper sulfate, copper oxide, 2,4-pentanedionate copper, trifluorene pendionate copper, and anhydrides and hydrates of the copper compounds Can also be used.

The phosphate copper compound of the present invention has, for example, a structure represented by the following formula (III) or (IV). In the formula (IV), the two phosphoric ester residues bonded to the copper ion may be the same or different.

Equation (I) Equation (I?)

〇

. \\ eight II ₂

ΧΟ-Ρ-0-Cu

Entering

X0 〇 0X

[However, X represents the same group as X in the formula (I). The reaction between the specific phosphoric acid group-containing compound and the copper ion supplying compound is carried out by bringing them into contact with each other under appropriate conditions. Specifically, o

(A) A specific phosphoric acid group-containing substrate and a copper ion supplying compound OP〇 = I are mixed and reacted.

X

How to make it 〇

X

(Mouth) a method of reacting a specific phosphoric acid group-containing compound with a copper ion supplying compound in an appropriate organic solvent,

(C) contacting an organic solvent layer in which a specific phosphoric acid group-containing compound is contained in an organic solvent with an aqueous layer in which a copper ion supplying compound is dissolved to form a specific phosphoric acid group-containing compound; Method for reacting a compound with a copper ion supplying compound

And so on.

The reaction conditions of the specific phosphoric acid group-containing compound and the copper ion supplying compound are as follows: a reaction temperature of 0 to 150 ° C., preferably 40 to 120 ° C .; 5 hours, preferably 1 to 10 hours.

The reaction ratio between the specific phosphoric acid group-containing compound and the copper ion supplying compound is such that the copper ion supplying compound is 0.3 to 1.0 mol per mol of the specific phosphoric acid group-containing compound. Is preferred.

The organic solvent used in the above method is not particularly limited as long as it can dissolve or disperse the specific phosphoric acid group-containing compound used. Examples thereof include benzene, toluene, and xylene. Aromatic compounds, methyl alcohol, Alcohols such as tyl alcohol and isopropyl alcohol; glycol ethers such as methyl sorb and ethyl sorb; ethers such as getyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and dimethoxetane; Examples include ketones such as methylethyl ketone, esters such as ethyl ethyl acetate, hexane, kerosene, and petroleum ether. It is also possible to use a polymerizable organic solvent such as (meth) acrylic acid esters such as (meth) acrylate, and aromatic vinyl compounds such as styrene and hexamethylstyrene. . Of these, toluene is preferred.

The organic solvent used in the method (c) is not particularly limited as long as it is insoluble or hardly soluble in water and can dissolve the specific phosphoric acid group-containing compound used. For example, among the organic solvents used in the method of (Mouth), aromatic compounds, ethers, esters, hexane, kerosene, (meth) acrylic esters, aromatic vinyl compounds And the like. In the reaction between a specific phosphoric acid group-containing compound and a copper ion supplying compound, an anionic acid component or water is released from the copper ion supplying compound. Such an acid component and water may reduce the moisture resistance and thermal stability of a composition containing a synthetic resin such as an acrylic resin, and may be removed as necessary. As a preferable method for removing the acid component and water, a specific phosphoric acid group-containing compound is reacted with a copper ion-supplying compound, and then the generated acid component and water (in the above method (mouth), The generated acid component, water and organic solvent] can be removed by distillation. In particular, when toluene or the like is used as the organic solvent in the method of (Port), volatile acid components and water can be efficiently removed by refluxing with a reflux device equipped with a water separator.

In the case of producing a phosphoric acid ester copper compound by the method (c), the following method can be mentioned as a preferable method for removing an acid component. After neutralization by adding an alkali component to an organic solvent layer containing a specific phosphoric acid group-containing compound in an organic solvent that is insoluble or hardly soluble in water, A specific phosphoric acid group-containing compound reacts with a copper ion-supplying compound by bringing the layer into contact with an aqueous layer in which the copper ion-supplying compound is dissolved, and then separating the organic solvent layer and the aqueous layer .

Here, examples of the aluminum component include sodium hydroxide, sodium hydroxide, and ammonia, but are not limited thereto.

According to such a method, a water-soluble salt is formed by the acid component and the alcohol component released from the copper ion-supplying compound, and the salt migrates to the aqueous layer, and the resulting phosphate ester is formed. Since the copper compound migrates to the organic solvent layer, the acid component can be removed by separating the aqueous layer and the organic solvent layer.

When the acid component does not cause any harm, the specific phosphoric acid group-containing compound is reacted with a copper ion supplying compound using a monomer or the like as a solvent, and the acid component is extracted without extraction according to the present invention. It can also be used as a monomer composition obtained by dissolving the phosphoric acid ester copper compound.

As described above, the ability to produce the phosphoric acid ester copper compound of the present invention, the phosphoric acid ester copper compound of the present invention comprises a specific phosphoric acid group-containing compound and a copper ion supplying compound. It is not limited to the compound represented by the above formula (III) or the above formula (IV) as long as it is obtained by the reaction. For example, a structure in which different copper ions are bonded to two hydroxyl groups in a monoester, a structure in which copper ion is bonded to only one of the two hydroxyl groups in a monoester, or a structure in which copper ion is bonded to a hydroxyl group in one ester Or a multimer containing two or more copper ions in the molecule or a coordination compound thereof.

The phosphoric acid ester copper compound of the present invention can efficiently and evenly cut near infrared rays, and such excellent near infrared absorption properties are not affected by ultraviolet rays. Since the phosphoric acid ester copper compound of the present invention contains an oxycarbonyl group in its molecular structure, it exhibits excellent solubility (compatibility) in a medium such as a resin component. Things.

Ku Metal Ion>

The resin composition of the present invention (the resin composition according to claim 51 and claim 52) is The polymer is composed of a phosphoric acid group and a metal ion mainly composed of copper ions.

Such a metal ion has an action of efficiently absorbing light in the near infrared region by interacting with a phosphoric acid group contained in the polymer.

Here, “having copper ions as a main component” means that the proportion of copper ions to all metal ions is 80% by mass or more. Specifically, it is a metal ion in which divalent copper ions and other metal ions are contained under conditions that satisfy the above ratio. When the proportion of copper ions is less than 80% by mass, the obtained resin composition does not efficiently absorb light in the near infrared region.

Here, as other metals constituting metal ions, sodium, potassium, potassium, iron, manganese, cobalt, magnesium, nickel and the like can be used according to the purpose.

In the resin composition of the present invention, the content ratio of metal ions containing copper ions as a main component is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer. And more preferably 0.1 to 15 parts by mass. If this ratio is less than 0.01 parts by mass, it is not possible to efficiently absorb light in the near infrared region, while if it exceeds 20 parts by mass, the dispersion of metal ions In some cases, transparency (visible light transmittance) may be impaired.

The resin composition of the present invention is configured such that a phosphoric acid group derived from a specific phosphoric acid group-containing compound is contained in a polymer together with a metal ion.

Examples of the method for introducing a phosphoric acid group into the polymer include the following methods [1] and [2] depending on the type of the specific phosphoric acid group-containing compound used.

[1] When the phosphoric acid group-containing compound is a polymerizable compound (monomer):

By polymerizing the phosphoric acid group-containing compound alone or by copolymerizing a mixed monomer composed of the phosphoric acid group-containing compound and a copolymerizable monomer, the phosphoric acid group is contained in the polymer structure. (Hereinafter, also referred to as “introduction method by monomer”.). Here, the polymerization treatment of the phosphoric acid group-containing compound or mixed monomer depends on the presence of metal ions. It is preferable to carry out the reaction below (that is, to react the phosphoric acid group-containing compound with the metal ion before the polymerization treatment), but it is also possible to carry out the reaction in a system in which the metal ion does not exist.

[2] When the phosphoric acid group-containing compound is a non-polymerizable compound:

A method of polymerizing a monomer composition containing a phosphoric acid group-containing compound and a monomer component (hereinafter, also referred to as “introduction method by adding a compound”).

Here, the polymerization treatment of the monomer composition is preferably performed in the presence of a metal ion (that is, a reaction between the phosphoric acid group-containing compound and the metal ion before the polymerization treatment). It can also be carried out in a system without ions.

''

When the “introduction method using a monomer” is employed as a method for introducing a phosphoric acid group into a polymer, a polymerizable compound is used as the specific phosphoric acid group-containing compound. Here, the specific phosphoric acid group-containing compound having polymerizability includes, as a group constituting a phosphoric acid ester bond [the group represented by (R) in the above formula (II)], “alkenylcarbonyl Examples of the compound include a phosphoric acid group-containing compound having an “alkoxyalkoxy group” or an “alkenyloxycarbonylalkoxy group”.

In the specific polymerizable phosphoric acid group-containing compound, the number of hydroxyl groups [the number represented by (n) in the above formula (II)] can be selected according to the resin composition molding method and the like. preferable.

Specifically, among the specific phosphoric acid group-containing compounds having a polymerizable unsaturated bond in the group represented by (R), a compound (diester) in which the value of n is 1 has a cross-linking polymerizability. It will be shown. On the other hand, a compound (monoester) in which the value of n is 2 has a high binding property to a metal ion. Therefore, when an optical filter is obtained by a molding method (injection molding / extrusion molding) applied to a thermoplastic resin, it is preferable to use a compound having a large mixing ratio of a compound having an n value of 2. When an optical filter is obtained by a casting method, a compound having a large mixing ratio of a compound having a value of n of 1 can be used.

In addition, a specific phosphoric acid group-containing compound in which the value of n is 1 When used in a molar ratio of 40:60 to 60:40, especially 45:55 to 55:45, the resulting monomeric compound It is preferable because metal ions can be uniformly contained in the body composition.

In the introduction method using a monomer, the “copolymerizable monomer” to be subjected to a copolymerization reaction with a phosphoric acid group-containing compound includes:

(1) homogeneously dissolving and mixing with a phosphate group-containing compound;

(2) good radical copolymerizability with a phosphate group-containing compound;

(3) The copolymer is not particularly limited as long as it satisfies that an optically transparent copolymer can be obtained by copolymerization with a phosphoric acid group-containing compound.

Specific examples of the copolymerizable monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, and n-propyl methacrylate. Rate, n—butyl acrylate, n—butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t—butynole methacrylate, n— Alkyl (meth) acrylate compounds such as hexyl acrylate, n-hexyl methacrylate, n-octyl acrylate, and n-octyl methacrylate

Glycidyl acrylate, glycidyl methacrylate, 2—hydroxyxyl acrylate, 2—hydroxyxyl acrylate, 2—hydroxypropyl acrylate, 2—hydroxy Modified alkyl (meth) acrylate compounds, such as propyl methyl acrylate, 2—hydroxybutyl acrylate, and 2—hydroxybutyl methacrylate

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dichloride, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate Relate, Polypropylene glycol dimethacrylate, 1,3—butylene glycol diacrylate, 1,3—Butyl glycol dimethacrylate, 1,4 Butanediol diacrylate, 1,4 —Butanediol dichloride, 1, 6 —Hexanediol diacrylate 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, 2-hydroxy-1,3, dimethacryloxypropane , 2,2—bis [4— (acryloxyethoxy) phenyl] propane, 2,2—bis [4— (methacryloxyethoxy) phenyl] propane, 2—hydroxy-1-acryl Roxy 1 3 — Me Kuri Roxyprono. Trimethylolpropane Reactor Retriate, Trimethylolpropane Reactor Rerate, Penyu Ellis Retriol React Rerate, Penyu Ellis Thritol Retrieve Rerate Polyfunctional (meta) acrylate compounds, such as pentaerythritol toltracetate, pentaerythritol toltracetate acrylate, acrylic acid, methacrylic acid, and 2-methacrylate Even carboxylic acids, such as cryloyloxetyl succinic acid, 2

Examples include aromatic vinyl compounds such as styrene, a-methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, divinylbenzene, vinylbenzoic acid, hydroxymethylstyrene, and trivinylbenzene.

These exemplified compounds can be used alone or in combination of two or more.

In the mixed monomer obtained from the phosphoric acid group-containing compound and the copolymerizable monomer, the ratio of the phosphoric acid group-containing compound to the copolymerizable monomer used is `` a phosphoric acid group-containing compound. The product: copolymerizable monomer (mass) "is preferably in the range of 3:97 to 90:10, and more preferably 10:90 to 80:20.

When the ratio of the phosphoric acid group-containing compound in the mixed monomer is less than 3% by mass, it is difficult to exhibit suitable light absorption characteristics in the obtained resin composition. On the other hand, when the ratio of the phosphoric acid group-containing compound in the mixed monomer exceeds 90% by mass, the viscosity of the mixed monomer becomes excessively high and the solubility of the metal ion may be impaired. In addition, the obtained resin composition may have low properties such as moisture resistance and hardness.

The polymerization treatment of the mixed monomer is preferably performed in the presence of a metal ion, that is, it is preferable to react the phosphoric acid group-containing compound with the metal ion before the polymerization treatment. As a result, the phosphoric acid group-containing compound (complex) coordinated with the metal ion is subjected to the polymerization reaction, and as a result, the dispersibility of the metal ion in the obtained polymer can be improved.

Specifically, a monomer composition containing a mixed monomer composed of a phosphoric acid group-containing compound and a copolymerizable monomer and a metal compound (hereinafter referred to as “monomer composition (A)”) ) Is prepared, and the monomer composition (A) is preferably subjected to a polymerization treatment.

The “metal compound” constituting the monomer composition (A) is a compound used to introduce a metal ion into a polymer obtained by polymerizing the monomer composition. For example, a metal ion (cation) And a counter ion (anion) of the metal ion.

Examples of the metal salt preferably used herein include a metal salt composed of a metal ion (cation) and an anion obtained by ionizing the following compound.

(Compounds serving as anion supply source)

Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, oxalic acid, nonanoic acid, decanoic acid, pendecanoic acid, lauric acid, myristic acid, palmitic acid, steariic acid Alkyl carboxylic acids with 1 to 18 carbon atoms, such as acid, halides of these acids, halides of rubonic acid (chlorides, bromides, fluorides), toluic acid, hydroxybenzoic acid, halides of benzoic acid (chloride) , Bromide, fluorinated), acetylsalicylic acid, nitrobenzoic acid, benzoic acid containing aromatic ring, phenyl acetic acid, c-cinnamic acid, dihydrocyanic acid, naphthyl acetic acid, naphthalene carboxylic acid, naphthylene dicarboxylic acid, etc. Ruponic acid having a naphthylene ring.

Further, as metal compounds (metal salts), metal chlorides, metal fluorides, metal oxides, metal nitrates, metal sulfates, metal salts of 2,4-pentanedionate, and metals of trifluorene pentagonate Salts, and anhydrides and hydrates thereof, can be exemplified.

The metal compounds that can be used in the present invention are not limited to the above compounds. In the monomer composition (A), the content ratio of the metal compound is such that the metal ion constituting the metal compound is 0.01 to 20 parts by mass per 100 parts by mass of the mixed monomer, Preferably, the ratio is 0.1 to 15 parts by mass.

When the ratio of the metal compound (metal ion) is too small, the resulting resin composition cannot sufficiently exhibit optical characteristics (for example, near-infrared cut function) by the metal ion. On the other hand, when the ratio of the metal compound (metal ion) is excessive, the metal ion is difficult to be uniformly dispersed in the obtained resin composition.

The method for preparing the monomer composition (A) is as follows. Before the radical polymerization of the mixed monomer comprising the phosphate group-containing compound and the copolymerizable monomer, the mixed monomer is prepared. A method in which the metal compound is added and dissolved and contained therein can be exemplified.

Here, the monomer composition (A) is prepared by mixing a phosphoric acid group-containing compound with a copolymerizable monomer to prepare a mixed monomer, and then adding the metal compound described above. Alternatively, the mixture may be prepared by mixing all of the phosphoric acid group-containing compounds and a part of the copolymerizable monomer, and then adding and mixing a metal compound. It may be prepared by adding the remainder of the copolymerizable monomer and mixing.

In addition, heating can be performed if necessary. Further, an antioxidant, an ultraviolet absorber, a light stabilizer, and other additives can be added to the monomer composition (A) as needed.

In the monomer composition (A) thus prepared, a complex is formed by coordinating the phosphoric acid group of the phosphoric acid group-containing compound with the metal ion of the metal compound. Thereby, the metal ion is dissolved in the composition.

When the “introduction method by adding a compound” is employed as a method for introducing a phosphoric acid group into a polymer, a non-polymerizable compound is used as a specific phosphoric acid group-containing compound.

Examples of the polymer which is a dispersion medium of the phosphate group-containing compound include acrylic resin, vinyl chloride resin, polycarbonate resin, polyester resin, and fluororesin. The resin composition is not particularly limited as long as it satisfies the optical characteristics required for the resin composition, but it is particularly preferable to use an acrylic resin.

Specific examples of the acryl-based monomer used to obtain the acryl-based resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and the like. n-Butyl acrylate, n-butyl methyl acrylate, isobutyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, t-butyl methacrylate, 2-ethyl Kisyl acrylate, 2 —ethylhexyl methacrylate, isodesyl acrylate, isodesylme acrylate, n — laurie crelate, n — laurie noremate, Tridecylacrylate, Tridecylmethacrylate, n—Stearylactylate, n—Stearylmethacrylate, Isobo Lunarcure rate, Isobornirme evening create, Metoxice tilua crerate, Metoxice tilmea evening create, Etoxosheilma create, Etkinje ilmeta create, Phenon Monofunctional (meta) acrylate compounds such as xicetyl acrylate and phenoxymethyl methacrylate can be used, and these can be used alone or in combination of two or more. be able to . In addition, a polyfunctional (meta) acrylate compound can be used as a part of the acrylic monomer, and specific examples thereof include ethylene glycol dimethacrylate and ethylene glycol. Glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4—butanediol dimethacrylate, 1,4—butanediol dimethacrylate, 2,2—bis ( 4 Ichime evening click Li Rokishe Tokishifuweniru) Pro c ⁼ down, Application Benefits main switch opening one Rupuroha. Entry rate, pen rate elimination rate meter rate, pen rate elimination rate rate rate, and the like. By using such a polyfunctional (meta) acrylate compound, the resulting acrylic resin has a cross-linked structure, so that it is a suitable mechanical filter as an optical filter. It has high characteristics.

The polymerization treatment of the monomer composition containing the non-polymerizable phosphoric acid group-containing compound and the monomer component is carried out in the presence of metal ions, that is, before the polymerization treatment, It is preferable to react the group-containing compound with the metal ion. As a result, the polymerization reaction of the monomer component proceeds in the presence of the complex in which the phosphoric acid group-containing compound is coordinated with the metal ion. As a result, the dispersion of the metal ion in the obtained polymer is performed. Performance can be improved.

Specifically, a monomer composition containing a phosphoric acid group-containing compound, a monomer component, and a metal compound (hereinafter, also referred to as “monomer composition (B)”) is prepared. The obtained monomer composition (B) is preferably subjected to a polymerization treatment. Here, examples of the “metal compound” include the same compounds (metal salts) as those constituting the monomer composition (A).

In the monomer composition (B), the content ratio of the metal compound is such that the metal ion constituting the metal compound is 0.01 to 20 parts by mass per 100 parts by mass of the monomer component, Preferably, the ratio is 0.1 to 15 parts by mass.

If the ratio of the metal compound (metal ion) is too small, the resulting resin composition cannot sufficiently exhibit the optical characteristics (for example, near-infrared cut function) of the metal ion. On the other hand, when the ratio of the metal compound (metal ion) is excessive, the metal ion is hardly uniformly dispersed in the obtained resin composition.

The proportion of the phosphoric acid group-containing compound in the monomer composition (B) is 3 to 50 parts by mass, preferably 3 to 30 parts by mass, per 100 parts by mass of the monomer component. It will be a ratio.

If the proportion of the phosphoric acid group-containing compound is too small, it becomes difficult to uniformly disperse the metal ions in the polymer, and the resulting resin composition may be opaque. On the other hand, if the proportion of the phosphoric acid group-containing compound is excessive, the mechanical properties required for the optical filter such as hardness may not be obtained.

In the monomer composition (B) prepared in this manner, a complex is formed by coordinating and bonding the phosphoric acid group of the phosphoric acid group-containing compound to the metal ion of the metal compound. Thereby, the metal ion is dissolved in the composition.

The phosphoric acid group-containing compound or the mixed monomer constituting the monomer composition (A) is By the cal-polymerization, a (co) polymer in which a phosphoric acid group is chemically bonded in a molecular structure (hereinafter, referred to as a “phosphoric acid group-containing (co) polymer”) is obtained.

The phosphoric acid group-containing (co) polymer contains the metal ions contained in the monomer composition (A) by retaining via the phosphoric acid group. . On the other hand, a polymer containing a phosphoric acid group-containing compound is obtained by radical polymerization of a monomer component constituting the monomer composition (B).

The polymer contains the metal ion contained in the monomer composition (B) by retaining the metal ion via the phosphate group.

The specific method of the radical polymerization treatment of the monomer composition is not particularly limited, and a radical polymerization method using a usual radical polymerization initiator, that is, a radical polymerization initiator is added to the monomer composition. A method of adding and polymerizing a monomer (mixed monomer or monomer component) under appropriate conditions, for example, a casting (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution. An overlay method such as a polymerization method can be used.However, when the obtained polymer has a crosslinked structure, it is difficult to melt-mold the polymer, so that it is used as a target optical product. It is preferable to employ a cast polymerization method which can directly obtain the following shape.

Here, as the radical polymerization initiator, various organic peroxide-based polymerization initiators can be used, but from the viewpoint that a polymer with little coloring can be obtained, t-butyl peroxy octanoate and t-butyl siloxane are used. Non-aromatic peroxyesters such as neodecaneate, t-butyl peroxypivalate, t-butyl peroxyl-2-ethyl ethylhexanoate, t-butyl peroxylaurate, lauroyl paroxylate, 3 It is preferred to use disilperoxide such as, 5,5—trimethylhexanoylperoxide. Also, 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2,4-dimethylpareronitrile) 1,1'-azobis (cyclohexane-2-carbotrilyl) An azo radical polymerization initiator such as) can also be preferably used.

Further, the radical polymerization reaction of the monomer can be carried out at the same reaction temperature and reaction time as in a normal radical polymerization reaction. The polymer obtained as described above [A phosphoric acid group-containing (co) polymer of the monomer composition (A). 'A polymer containing a phosphoric acid group-containing compound of the monomer composition (B)] [Coalescing] can be used as it is, or formed into a desired shape such as film, sheet, plate, column, lens, etc., and polished to obtain various optical filters. Optical materials · Can be used as optical components.

The embodiments of the present invention have been described above. However, the present invention is not limited to these embodiments, and various modifications can be made as described below.

(1) A phosphoric acid group-containing compound (non-polymerizable compound) coordinated to a metal ion is added to the polymer and mixed, so that the phosphoric acid group and the metal ion are added to the polymer. It may be introduced to constitute the resin composition.

(2) By adding and mixing a metal compound into a polymer containing a phosphoric acid group, a metal ion may be introduced into the polymer to form a resin composition.

Then, a phosphoric acid group derived from a phosphoric acid group-containing compound having an oxycarbonyl group (C 00— or 0 C 0—) and a metal ion held by the phosphoric acid group are contained in the polymer. All of the resin compositions contained in the present invention are included in the scope of the present invention.

The resin composition of the present invention can be applied to various uses as described below due to its excellent optical properties (efficient and uniform cutting function of light in the near infrared region).

The optical filter composed of the resin composition of the present invention is preferably used as a luminosity correction filter for a light-receiving element (for example, a photoelectric conversion element composed of a silicon photodiode) in a photometric unit of a power lens. Can be used.

Here, the `` visibility correction filter for the light receiving element '' includes a convergence lens, etc., in addition to the visibility correction filter that is arranged alone in the optical path to the light receiving element .

According to the camera equipped with the optical filter made of the resin composition of the present invention, the light incident on the light receiving element (silicon photodiode) can be substantially limited to light in the visible region. As a result, accurate photometry (exposure operation) can be performed. The optical filter made of the resin composition of the present invention is preferably used as a visibility correction filter for a CCD (for example, a photoelectric conversion element made of a silicon photodiode) in an imaging device (image input device). Can be.

Here, the `` visibility correction filter for CCD '' includes the sight sensitivity correction filter that is placed alone in the optical path to the CCD, as well as the lizard, lens, and protective plate. I do.

In addition, imaging devices equipped with CCDs include video cameras and digital cameras.

Three

Cameras, board cameras, color scanners, color facsimiles, color copiers, and color telephones can be mentioned.

According to the imaging apparatus equipped with the optical filter made of the resin composition of the present invention, the light incident on the CCD (silicon photodiode) can be substantially limited to light in the visible region. As a result, accurate photometry (exposure operation) can be performed, and the reproduction of the red component is not hindered.

The optical filter comprising the resin composition of the present invention can be suitably used as a visibility correction filter for an imaging device (image input device) equipped with a CMOS image sensor or an artificial retina. .

According to the CMOS image sensor and the artificial retina provided with the optical filter made of the resin composition of the present invention, and the imaging device equipped with these, the same effects as those of the above-mentioned CCD can be obtained.

The optical filter comprising the resin composition of the present invention is suitably used as a noise filter in an environment where an infrared communication device (a communication device using light of 850 to 950 nm as a medium) is used. Can be used. According to such a noise cut filter, a source of near-infrared rays (for example, a machine using near-infrared rays such as an automatic door or a remote controller) is covered, and infrared rays from the source are cut off to thereby prevent noise during communication. Can be reliably prevented.

Further, by disposing an optical filter made of the resin composition of the present invention on the front surface of a panel of a plasma display device, the near-infrared light emitted from the panel can be obtained. Lines can be cut efficiently. As a result, a malfunction of the remote controller due to near-infrared rays does not occur around the plasma display device.

The optical filter made of the resin composition of the present invention is used as a heat ray absorbing filter, specifically, a window material in a building such as a house or a building, a window material of an automobile or a train car, or a translucent member of a greenhouse. It can be suitably used as a lighting cover or the like.

The optical filter comprising the resin composition of the present invention can be suitably used as a constituent material of an optical fiber. Further, such an optical filter may be provided in a lighting part of the optical fiber device.

The optical filter comprising the resin composition of the present invention can be suitably used as a spectacle lens. According to such a spectacle lens, eyes can be reliably protected from heat rays and near infrared rays which cause cataracts.

<Near infrared absorbing powdery substance

The powdery substance of the present invention comprises the phosphoric acid ester copper compound of the present invention. Since the powdery substance of the present invention can efficiently cut light in the near-infrared region, it can be used as it is as a near-infrared absorber. Moreover, the powdery substance of the present invention has good dispersibility or solubility in a medium, and can be used in a wide range of fields together with such a medium or alone.

By storing the powdery substance of the present invention in a cell made of transparent glass or the like, a near-infrared absorbing member can be formed. Further, by mixing the powdery substance of the present invention with a coating agent, a bonding agent, or an adhesive, a coating film, an adhesive layer, or an adhesive layer having near-infrared absorbing property or heat ray absorbing property can be used as a wall material, a window material, or the like. It can also be formed on the surface of a substrate (eg, film substrate, substrate). Furthermore, after dissolving the powdery substance of the present invention in an appropriate solvent and applying it to the surface of the substrate, the solvent is evaporated off to form a near-infrared absorbing layer on the surface of the substrate. it can.

Here, the solvent for the powdery substance of the present invention includes water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol; glycol ethers such as methylcellosolve and ethylcellosolve; Ethers such as mono-ter, diisopropyl ether, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, esters such as ethyl ethyl acetate, isopropyl acetate, butyl acetate, butyl acetate, etc. Benzene, toluene, xylene and the like, hexane, kerosene, petroleum ether and the like. Further, organic solvents having polymerizability such as (meth) acrylic acid esters such as (meth) acrylate, and aromatic vinyl compounds such as styrene and α-methylstyrene can be used. .

Near infrared absorbing liquid material>

The liquid substance of the present invention comprises the phosphoric acid ester copper compound of the present invention. Since the liquid substance of the present invention can efficiently cut light in the near infrared region, it can be used as it is as a near infrared absorber. Moreover, the liquid substance of the present invention has good dispersibility or solubility (compatibility) in a medium, and the liquid substance of the present invention, which can be used in a wide range of fields together with such a medium or alone, A near-infrared absorbing member (liquid cell) can be configured by being housed in a cell made of transparent glass or the like. Further, by mixing the liquid substance of the present invention into a coating agent, an adhesive, or an adhesive, a coating film, an adhesive layer, and an adhesive layer having near-infrared absorbing property or heat ray absorbing property can be used as a base material such as a wall material or a window material. It can also be formed on the surface of a material (for example, a film substrate or substrate). Furthermore, the liquid substance of the present invention is applied alone or after being dissolved in an appropriate solvent and applied to the surface of the substrate, and then the solvent is removed by evaporation to form a near-infrared absorbing layer on the surface of the substrate. It can also be formed. Here, the solvent for the liquid substance of the present invention is not particularly limited as long as it has compatibility with the liquid substance. For example, the solvent for the powdery substance of the present invention is exemplified. Solvents used can be used.

NIR-absorbing paste-like substance>

The paste-like substance of the present invention comprises the phosphoric acid ester copper compound of the present invention. Since the paste-like substance of the present invention can efficiently cut light in the near infrared region, it can be used as it is as a near infrared absorber. Further, the paste-like substance of the present invention has good dispersibility or solubility (compatibility) in a medium, and can be used in a wide range of fields together with such a medium or alone.

The near-infrared absorbing member can be configured by housing the paste-like substance of the present invention in a cell made of transparent glass or the like. Further, by mixing the paste-like substance of the present invention into a coating agent, an adhesive, or an adhesive, a coating film having a near-infrared absorbing property or a heat ray absorbing property, an adhesive layer, an adhesive layer is used as a wall material, a window material, or the like. It can also be formed on the surface of a substrate (eg, a film substrate or substrate). Furthermore, the paste-like substance of the present invention is applied alone or after dissolving in an appropriate solvent to the surface of a substrate, and then the solvent is evaporated off to form a near infrared absorbing layer on the surface of the substrate. Can also be formed.

Here, the solvent for the paste-like substance of the present invention is not particularly limited as long as it has compatibility with the paste-like substance. For example, for the powder-like substance of the present invention, The solvents exemplified above can be used.

The composition of the present invention contains the phosphoric acid ester copper compound of the present invention. According to the composition of the present invention, light in the near infrared region can be efficiently and uniformly cut. Can be.

The properties of the composition of the present invention are not particularly limited, such as solid, liquid, and base. The constituent components other than the phosphoric acid ester copper compound are not particularly limited.

The liquid composition of the present invention (liquid composition) is prepared by dissolving the phosphoric acid ester copper compound of the present invention (powder substance, liquid substance, paste substance) in an appropriate solvent. can do.

The liquid composition of the present invention may be transparent, opaque, or translucent, and can efficiently and uniformly cut light in the near-infrared region in any state.

By containing the liquid composition of the present invention in a cell made of transparent glass or the like, A near-infrared absorbing member (liquid cell) can be configured.

Examples of the solvent constituting the liquid composition of the present invention include water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, glycol ethers such as methylcellosolve and ethylcellosolve, and geethylether. , Diisopropyl ether and other ethers, acetone, methylethylketone, methylisobutylketone, cyclohexanone and other ketones, ethyl acetate, isopropyl acetate, butyl acetate, and butyl acetate. Esters, benzene, toluene, xylene, and other aromatic compounds; hexane, kerosene, petroleum ether, and the like. Also, a polymerizable organic solvent such as an aromatic vinyl compound such as (meth) acrylic acid ester such as (meth) acrylate, styrene, and hexamethylstyrene can be used. These can be used alone or in combination of two or more.

<Monomer composition

The composition of the present invention may contain a monomer.

Here, the monomers constituting the composition (monomer composition) of the present invention include: 丄. A specific phosphoric acid group-containing compound having polymerizability, g. Acid ester copper compounds and other monomers can be mentioned.

Here, the “other monomer” is contained as a copolymerizable monomer together with the above (1) and (2) or the above compound (monomer), When none of the monomers is contained (when the phosphate copper compound of the present invention is non-polymerizable), it is contained as a monomer component.

Specific examples of the above “other monomers” include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n— Propyl methacrylate, n-butyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate Alkyl (meta) acrylates such as octyl acrylate,

Glycidyl acrylate, Glycidylmethacrylate, 2 Hydroxyshetyla Crylate, 2 hydroxypropyl acrylate, 2 hydroxypropyl acrylate, 2 hydroxypropyl acrylate, 2 hydroxybutyl acrylate, 2 hydrate Monofunctional (meta) acrylates such as modified alkyl (meth) acrylates, such as droxybutylmethacrylate:

Ethylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diethylene glycol, polyethylene glycol diacrylate, polyethylene glycol diethylene glycolate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate Polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,4 butanediol dimethacrylate, 1,4-hexanediol dihydrate, 1,6 hexanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethylate, neopentyl glycol dimethacrylate Rate, 2 Hydroxy 1.3 dimethacryloxypropane, 2,2 bis [4 (methacryloxyethoxy) phenyl] prono. , 2 hydroxy 1 acryloxy 3 meth yl oxypro han, trimethylol lip mouth trimethyl acrylate, trimethylolpropane acrylate, pen erythrite Tri-rate rate, Pen-time rate rate, Pen-time rate rate rate, Pen-time rate rate rate, Pen-time rate rate rate, etc. Polyfunctional (meta) acrylates;

Carboxylic acids such as acrylic acid, methyl carboxylic acid, 2-methyl chloroyloxetyl succinic acid, and 2 methacryloyl oxethyl sulfonic acid;

Examples include aromatic vinyl compounds such as styrene, permethylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, divinylbenzene, vinylbenzoic acid, hydroxymethylstyrene, and trivinylbenzene. These monomers can be used alone or in combination of two or more.

The composition of the present invention may be a polymer composition containing a polymer (resin). . As a method for introducing a polymer into the composition of the present invention, the following method can be mentioned.

(1) A monomer composition obtained by dissolving a specific phosphoric acid group-containing compound and a copper ion supplying substrate in a polymerizable monomer is polymerized.

(2) A monomer composition obtained by dissolving the phosphoric acid ester copper compound of the present invention in a polymerizable monomer is polymerized.

(3) After dissolving a specific phosphoric acid group-containing compound and a copper ion supplying compound in a polymer solution obtained by dissolving the polymer in an appropriate solvent, the solvent is removed.

(4) After dissolving the ester copper phosphate compound of the present invention in a polymer solution obtained by dissolving the polymer in an appropriate solvent, the solvent is removed.

(5) Add the phosphate copper compound of the present invention to the polymer melted by heating and dissolve

In the polymer (for example, acrylic resin) constituting the polymer composition of the present invention, a phosphoric acid group derived from a specific phosphoric acid group-containing compound and a copper ion from a copper ion supplying compound are formed. The copper ion is contained in the polymer via a phosphoric acid group by an ionic bond or a coordinate bond.

Then, the polymer composition having copper ions retained through a phosphate group has a characteristic absorption characteristic in the near infrared region. Further, since the copper ion and the phosphate group are coordinated to form a complex, the copper ion is contained in a state of being uniformly dispersed in the polymer component, and the resulting polymer composition The object has good transparency.

Coating agent>

The coating material of the present invention is a processed material having near-infrared absorptivity which comprises the composition of the present invention (a liquid composition or a paste-like composition).

The coating agent of the present invention can be prepared by dissolving or dispersing the phosphoric acid ester copper compound of the present invention in an appropriate coating agent. The coating agent of the present invention may be an oily coating agent or an aqueous coating agent. Further, the coating composition of the present invention may contain additives such as an ultraviolet absorber and an antioxidant. The application of the coating composition of the present invention is not particularly limited as long as it is intended for coating the surface of a substrate. According to the coating composition of the present invention, a coating film having near-infrared absorption is formed. can do.

Here, as a method for preparing the oil-based coating agent, a method in which the phosphoric acid ester copper compound of the present invention is dissolved in an organic solvent together with a Baying resin can be mentioned.

The binder resin that constitutes the oil-based coating agent includes an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, and an aliphatic polyolefin resin. Resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, modified polyvinyl resins, and copolymer resins thereof. Organic solvents constituting the oil-based coating agent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixed solvents thereof. Can be mentioned. The content of the phosphoric acid ester copper compound in the oil-based coating agent varies depending on the thickness of the coating film (surface coating layer), the desired near-infrared cut rate, the desired visible light transmittance, and the like. The amount is usually 0.1 to 100 parts by weight with respect to 100 parts by weight of the binder resin. The content of the binder resin in the coating composition is usually 1 to 50% by weight.

On the other hand, as a method for preparing an aqueous coating agent, the phosphoric acid ester copper compound of the present invention is finely pulverized to obtain fine particles of several micrometers or less, and the fine particles are uncolored acrylic polymer polymer. A method of dispersing in a marsion can be mentioned. <Adhesive>

The pressure-sensitive adhesive of the present invention is a processed material having near-infrared absorptivity which comprises the composition of the present invention (a liquid composition or a paste-like composition).

The pressure-sensitive adhesive of the present invention can be prepared by dissolving or dispersing the phosphoric acid ester copper compound of the present invention (powder substance, liquid substance, paste substance) in a suitable adhesive medium. .

The term "adhesive medium" used herein includes silicone-based, urethane-based, and acrylic-based adhesive components for resins, and polyvinyl butyral adhesive for laminated glass. δ 1

(PVB) and a known adhesive having transparency such as an ethylene-vinyl acetate adhesive (EVA).

In addition, as a method for dissolving and dispersing the phosphoric acid ester copper compound, a method of dissolving and dispersing the copper compound by adding it directly to a viscous medium; A method of adding and dissolving an acid ester copper compound and then evaporating and removing the solvent can be mentioned. Here, the content ratio of the phosphoric acid ester copper compound in the pressure-sensitive adhesive of the present invention varies depending on the thickness of the pressure-sensitive adhesive layer to be formed, and is, for example, 0.1 to 80% by weight.

The use of the pressure-sensitive adhesive of the present invention is not particularly limited. For example, a near-infrared-absorbing transparent seal can be produced by applying the pressure-sensitive adhesive of the present invention to a surface such as a transparent sheet. The pressure-sensitive adhesive of the present invention can also form an intermediate layer of a near-infrared absorbing film described later or a near-infrared absorbing plate.

Adhesive

The adhesive of the present invention is a processed material having near-infrared absorbing properties, comprising the composition of the present invention (liquid composition or paste-like composition).

The adhesive of the present invention can be prepared by dissolving or dispersing the phosphoric acid ester copper compound (powder substance, liquid substance, paste-like substance) of the present invention in an appropriate adhesive medium. it can.

<Near-infrared absorbing film>

The near-infrared absorbing film of the present invention includes the following films.

(1) A film ('cast film) comprising the composition of the present invention.

(2) A film obtained by forming a near-infrared absorbing layer comprising the powdery substance of the present invention on the surface of a film substrate.

(3) A film obtained by forming a near-infrared absorbing layer comprising the paste-like substance of the present invention on the surface of a film substrate.

(4) A film obtained by applying the coating composition of the present invention to the surface of a film substrate. (5) A film obtained by applying the monomer composition of the present invention to the surface of a film substrate, followed by drying and polymerization. (6) A film comprising a composite film having an intermediate layer (near-infrared absorbing layer) comprising the powdery substance of the present invention.

(7) A film comprising a composite film having an intermediate layer (near-infrared absorbing layer) comprising the pasty substance of the present invention.

(8) A film comprising a composite film having an intermediate layer formed from the adhesive of the present invention. (9) A film comprising a composite film having an intermediate layer formed from the pressure-sensitive adhesive of the present invention. Examples of the film substrate constituting the film of (2) to (5) include polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, and polycarbonate. Examples thereof include transparent base materials such as krill resin and polystyrene resin.

Examples of the method of applying the coating agent to the film base include a coating method using a bar coater, a blade coater, a spin coater, a reverse coater, a die coat and the like, and a spraying method. be able to.

In addition, a protective layer may be provided on the application surface to protect the application surface (near-infrared absorbing layer), and a transparent resin plate or a transparent resin film may be attached to the application surface. You can also match.

The films (8) to (9) can be produced by bonding a transparent film (resin film) with the adhesive or pressure-sensitive adhesive of the present invention. The intermediate layer (adhesive or sticky layer) acts as a near infrared absorbing layer. According to the film of the present invention, light in the near-infrared region can be efficiently and evenly cut, and only a simple operation of sticking to an appropriate place can provide good near-infrared light in the sticking region. It can exhibit infrared absorption performance.

The near infrared absorbing plate of the present invention includes the following plate-like bodies.

(1) A plate comprising the composition of the present invention.

(2) A plate obtained by forming a near-infrared absorbing layer comprising the powdery substance of the present invention on the surface of a substrate.

(3) forming a near-infrared absorbing layer comprising the paste-like substance of the present invention on the surface of the substrate; The resulting plate.

(4) A plate obtained by applying the coating composition of the present invention to the surface of a substrate.

(5) A plate obtained by applying the monomer composition of the present invention to the surface of a substrate, followed by drying and polymerization.

(6) A composite plate having an intermediate layer formed from the adhesive of the present invention.

(7) A composite plate having an intermediate layer formed from the pressure-sensitive adhesive of the present invention.

(8) A plate-like body in which a resin plate and a resin film are joined via an intermediate layer.

(9) A plate-like body in which a glass plate and a resin film are joined via an intermediate layer.

Examples of the substrate constituting the near-infrared absorbing plate of the above (2) to (5) include a resin plate and a glass plate.

The near-infrared absorbing plate of (6) to (7) includes a composite plate in which resin plates are joined through an intermediate layer, a composite plate in which glass plates are joined through an intermediate layer, A composite plate in which a glass plate and a resin plate are joined via an intermediate layer is included. <'Near infrared absorbing material>

The near-infrared absorbing member of the present invention comprises the phosphoric acid ester copper compound of the present invention (powder substance, liquid substance, paste-like substance) or the composition of the present invention (liquid composition, paste-like composition). _C contained in the cell

The shape and material of the cell constituting the near-infrared absorbing member are not particularly limited as long as it has a space (gap) for accommodating the phosphoric acid ester copper compound of the present invention or the composition of the present invention. Instead, for example, there can be mentioned one in which an accommodation space is formed by partition walls made of transparent glass.

The use of the near-infrared absorbing member of the present invention is not particularly limited.

(Heat ray absorption filter).

Optical File Yuichi>

The optical filter of the present invention is obtained from the phosphoric acid ester copper compound of the present invention or the composition of the present invention.

As the “optical filter obtained from the phosphoric acid ester copper compound of the present invention”, the phosphoric acid ester copper compound of the present invention (powder substance, liquid substance, paste substance) An optical filter comprising a film having a near-infrared absorbing layer formed from (a near-infrared absorbing film of the present invention);

2. An optical filter comprising a plate-like body (near-infrared absorbing plate of the present invention) having a near-infrared absorbing layer formed from the phosphoric acid ester copper compound of the present invention (powder substance / liquid substance 'paste-like substance) Luther,

An optical filter comprising the near-infrared absorbing member of the present invention in which the phosphoric acid ester copper compound of the present invention (powder substance, liquid substance, paste-like substance) is accommodated in a cell can be mentioned.

Further, the optical filter obtained from the composition of the present invention is processed by using the optical filter comprising the composition of the present invention and the composition of the present invention (coating agent, adhesive, adhesive). The resulting film-like or plate-like optical filter (near-infrared ray absorbing film, near-infrared ray absorbing plate, near-infrared ray absorbing member) is included.

According to the optical filter of the present invention, light in the near-infrared region can be efficiently and evenly cut, and the visibility correction filter, the noise cut filter, the heat ray absorption filter, and the plasma display panel can be cut. It can be suitably used as a front plate or the like.

The optical fiber of the present invention is composed of the composition of the present invention. Further, the optical fiber device of the present invention is configured such that the optical filter of the present invention is provided in a lighting part. That is, the composition of the present invention can be suitably used as a constituent material of an optical fiber, and the optical filter of the present invention can be provided in a lighting part of the optical fiber.

ADVANTAGE OF THE INVENTION According to the optical fiber and the optical fiber device of this invention, since a heat ray can be cut at the time of optical transmission, the rise in room temperature can be suppressed.

Glasses Lens>

The spectacle lens of the present invention is obtained from the composition of the present invention.

ADVANTAGE OF THE INVENTION According to the spectacle lens of this invention, since the near infrared rays harmful to a photoreceptor cell are cut, the aging of a photoreceptor cell can be prevented and an eye failure (for example, cataract) can be prevented. Plasma display device>

The plasma display device of the present invention is configured by disposing the optical filter of the present invention on the front surface of the panel.

By arranging the optical filter of the present invention on the front surface of the panel of the plasma display device, it is possible to efficiently cut the near-infrared rays emitted from the panel. As a result, a malfunction of the remote controller due to the near-infrared ray and a trouble in infrared communication do not occur around the plasma display device.

The camera of the present invention is configured by mounting the optical filter (visibility correction filter) of the present invention.

ADVANTAGE OF THE INVENTION According to the camera of this invention, the human light to a light receiving element can be substantially limited to the light of a visible region, As a result, accurate photometry (exposure operation) can be performed. <CCD camera and image input device>

The CCD camera of the present invention is configured by mounting the optical filter (visibility correction filter) of the present invention.

The image input device (imaging device) of the present invention is configured by mounting the CCD camera of the present invention. The image input device of the present invention includes, for example, a video camera, a digital camera, a board camera, a color scanner, a color fax, a color copier, a color television telephone device, and the like.

According to the image input device of the present invention, light incident on a CCD (for example, a silicon photodiode) can be substantially limited to light in a visible region, and as a result, accurate photometry (exposure operation) is performed. In addition, the reproduction of the red component and the color balance are not hindered.

C CMOS image sensor '' Image input device>

The CMOS image sensor of the present invention is configured by mounting the optical filter (visibility correction filter) of the present invention.

An image input device (imaging device) of the present invention includes the above-described CMOS image sensor. It is composed.

According to the image input device equipped with the CMOS image sensor of the present invention (the image input device of the present invention), the same effects as those of the above-described CCD can be obtained.

Artificial retina · Image input device>

The retinal prosthesis of the present invention is configured by mounting the optical filter (visibility correction filter) of the present invention.

An image input device (imaging device) of the present invention is configured by mounting the above artificial retina.

According to the image input device equipped with the artificial retina of the present invention (the image input device of the present invention), the same effect as the above-described effect in CCD can be obtained.

',': Infrared communication environment maintenance device>

The infrared communication environment maintenance device of the present invention is configured by mounting the noise cut filter of the present invention.

ADVANTAGE OF THE INVENTION According to the infrared communication environment maintenance apparatus of this invention, in the infrared communication which uses a wavelength of 800-10000 nm as a medium, the light source of the said wavelength range (for example, automatic door, radio control) The noise that occurs can be efficiently exploited, and communication failures caused by the noise can be reliably prevented.

The partition wall or window material for partitioning the room with the infrared communication device is composed of the phosphoric acid ester copper compound of the present invention or the composition of the present invention, or the partition wall or window material for partitioning the room with the infrared communication device. By applying the phosphoric acid ester copper compound (liquid substance / paste substance) or the composition (coating agent / adhesive / adhesive) of the present invention to the surface of It is possible to reliably prevent the resulting communication failure.

Window material>

The window material of the present invention comprises a heat ray absorbing filter.

Examples of the form of the window material of the present invention include a window material in a building such as a house or a building, a window material of a car or a train car, a translucent member of a greenhouse for agriculture, and a lighting cover. Can be Brief explanation of drawings

FIG. 1 is a curve diagram showing a spectral absorption spectrum of the near-infrared absorbing plate according to the first embodiment.

FIG. 2 is a curve diagram showing the spectral absorption spectrum of the near-infrared absorbing plate according to Example 2.

FIG. 3 is a curve diagram showing a spectral absorption spectrum of the near-infrared absorbing plate according to the third embodiment.

FIG. 4 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 4. FIG. 5 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 5. FIG. 6 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 6. FIG. 7 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 7. FIG. 8 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 8. FIG. 9 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 9. FIG. 10 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Example 10.

FIG. 11 is a curve diagram showing the spectral absorption spectrum of the liquid composition according to Comparative Example 1. FIG. 12 is a curve showing the spectral transmission spectrum of the near-infrared absorbing plate according to Example 11. It is a figure.

FIG. 13 is a curve diagram showing a spectral transmission spectrum of the near-infrared absorbing member according to Example 12.

FIG. 14 is a curve diagram showing the spectral transmission spectrum of the near-infrared absorbing plate according to Example 13. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, examples of the present invention will be described, but the present invention is limited by these. Not something.

In the following, “parts” means “parts by mass”.

<Example 1

0.23 g of an equimolar mixture of a specific phosphoric acid group-containing compound represented by the following formula (1) and a specific phosphoric acid group-containing compound represented by the following formula (2): After dissolving 0.16 g of the hydrate in 2 O ml of methyl ethyl ketone, the methyl ethyl ketone was distilled off from the solution to obtain a powdery phosphoric acid ester copper compound (the phosphoric acid of the present invention). An ester copper compound) was prepared.

A near-infrared absorbing layer of the present invention was manufactured by forming a near-infrared absorbing layer comprising the obtained phosphoric acid ester copper compound on the surface of the slide glass.

With respect to the obtained near-infrared absorbing plate, a spectral absorption spectrum (400 to 900 nm) using reflected light was measured. The results are shown in Figure 1.

As shown in FIG. 1, it is understood that the near-infrared absorbing plate obtained in Example 1 efficiently absorbs light in a near-infrared region (800 to 900 nm).

Expression

formula

0.32 g of an equimolar mixture of a specific phosphoric acid group-containing compound represented by the following formula (3) and a specific phosphoric acid group-containing compound represented by the following formula (4): After dissolving 0.16 g of the hydrate in 20 ml of methylethylketone, the methylethylketone was distilled off from this solution to obtain a powdery phosphoric acid copper ester compound (the present invention). (A copper phosphate compound) was prepared.

With respect to the obtained near-infrared absorbing plate, a spectral absorption spectrum (400 to 900 nm) using reflected light was measured. The result is shown in figure 2.

As shown in FIG. 2, it is understood that the near-infrared absorbing plate obtained in Example 2 efficiently absorbs light in the near-infrared region (800 to 900 nm). Equation (3)

H C— — C Jrt

C-1 0— CH ₂ -CH 0-P -〇一

II!

0 CH ₂ C 1 OH

HC— ^— C n.

I

-CH-CH ₂ one 0- c

I II CH ₂ C 1 〇

Equation (4)

HC

K-Example 3>

0.29 g of an equimolar mixture of a specific phosphoric acid group-containing compound represented by the following formula (5) and a specific phosphoric acid group-containing compound represented by the following formula (6): After dissolving 0.16 g of the hydrate in 20 ml of methylethylketone, the methylethylketone was distilled off from this solution to obtain a powdery phosphoric acid ester copper compound (the phosphorus of the present invention). Acid copper ester compound) was prepared.

With respect to the obtained near-infrared absorbing plate, a spectral absorption spectrum (400 to 900 nm) using reflected light was measured. The results are shown in Figure 3.

As shown in FIG. 3, it is understood that the near-infrared absorbing plate obtained in Example 3 efficiently absorbs light in the near-infrared region (800 to 900 nm). Equation (5)

0 CH ₂ CH _: OH

H ₂ C = C-CH _:

I

-CH-CH ₂ one 〇- C

I II CH ₂ CH ₃ 〇 Equation (6)

Example 4

0.24 g of an equimolar mixture of a specific phosphoric acid group-containing compound represented by the following formula (7) and a specific phosphoric acid group-containing compound represented by the following formula (8): By dissolving 0.16 g of the hydrate in 20 ml of methylethylketone, a solution of an ester copper phosphate compound (the liquid composition of the present invention) was prepared.

With respect to the obtained liquid composition, a spectral absorption spectrum (400 to 1200 nm) having an optical path length of 1 Omm was measured. Fig. 4 shows the results.

As shown in FIG. 4, it is understood that the liquid composition obtained in Example 4 efficiently absorbs light in the near infrared region (800 to 100 nm). Equation (7)

H 3 H 2 C = CH1 CH3

II CH-CH ₂ one 0- C

II

0 Equation (8)

0.29 g of an equimolar mixture of the specific phosphoric acid group-containing compound represented by the above formula (5) and the specific phosphoric acid group-containing compound represented by the above formula (6), and copper acetate monohydrate By dissolving 0.16 g of the hydrate in 2 O ml of methyl ethyl ketone, a solution of an ester copper phosphate compound (the liquid composition of the present invention) was prepared.

With respect to the obtained liquid composition, a spectral absorption spectrum (400 to 1200 nm) having an optical path length of 1 Omm was measured. Fig. 5 shows the results.

As shown in FIG. 5, it is understood that the liquid composition obtained in Example 5 efficiently absorbs light in the near infrared region (800 to 100 nm).

0.38 g of an equimolar mixture of a specific phosphoric acid group-containing compound represented by the following formula (9) and a specific phosphoric acid group-containing compound represented by the following formula (10): By dissolving 0.16 g of the hydrate in 20 ml of methylethylketone, a solution of the ester copper phosphate compound (the liquid composition of the present invention) was prepared. For the obtained liquid composition, a spectral absorption spectrum (400 to 1200 nm) having an optical path length of 10 mm was measured. Fig. 6 shows the results.

As shown in FIG. 6, it is understood that the liquid composition obtained in Example 6 efficiently absorbs light in the near infrared region (800 to 100 nm) as shown in FIG. .

c

Equation (9) H

Four

One CH3

Expression (10)

H ₂ C = C-CH _; 0

II

-O-C-Cs H O-P-OH

II

0 OH

0.73 g of an equimolar mixture of a specific phosphoric acid group-containing compound represented by the following formula (11) and a specific phosphoric acid group-containing compound represented by the following formula (12): By dissolving 0.16 g of monohydrate in 20 ml of methyl ethyl ketone, a solution of a copper ester phosphate compound (a liquid composition of the present invention) was prepared.

With respect to the obtained liquid composition, a spectral absorption spectrum (400 to 1200 nm) having an optical path length of 10 mm was measured. Fig. 7 shows the results.

As shown in FIG. 7, it is understood that the liquid composition obtained in Example 7 efficiently absorbs light in the near-infrared region (800 to 100 nm). Equation (1 1)

1.1 g of an equimolar mixture of the specific phosphoric acid group-containing compound represented by the above formula (7) and the specific phosphoric acid group-containing compound represented by the above formula (8), and copper benzoate anhydrous 0.612 g of the product in 10 ml of methyl methacrylate (MMA) to prepare a monomer solution of the phosphoric acid ester copper compound (the liquid composition of the present invention). did. For the obtained liquid composition, a spectral absorption spectrum (400 to 1500 nm) having an optical path length of 1 mm was measured. Fig. 8 shows the results.

In the spectral absorption spectrum shown in FIG. 8, the maximum absorbance is 0.42 (820 nm :), and the liquid composition obtained in Example 8 is in a near infrared region (800 to 100 nm). It is understood that light of (0 nm) is efficiently absorbed.

In the spectral absorption spectrum shown in FIG. 8, the absorbance (A _s ) at 800 nm is 0.4, and the absorbance (A,) at 100 nm is 0.32. The ratio of the two (A, „. ZA _{8 U.} ) is 0.80, and according to this liquid composition, light in the near-infrared region can be cut evenly (can be well balanced). It is understood that. 6 δ

1.3 g of an equimolar mixture of the specific phosphoric acid group-containing compound represented by the above formula (5) and the specific phosphoric acid group-containing compound represented by the above formula (6), and copper benzoate anhydrous Of the compound (0.61 g) was dissolved in 10 ml of methyl methacrylate (MMA) to prepare a monomer solution of the phosphoric acid ester copper compound (the liquid composition of the present invention). . For the obtained liquid composition, a spectral absorption spectrum (400 to 1500 nm) having an optical path length of 1 mm was measured. Fig. 9 shows the results.

In the spectral absorption spectrum shown in FIG. 9, the maximum absorbance is 0.41 (824 nm), and the liquid composition obtained in Example 9 is in the near infrared region (800 to 100000). It is understood that the light of (nm) is efficiently absorbed.

In the spectral absorption spectrum shown in FIG. 9, the absorbance at 800 nm (Au.) Is 0.41 and the absorbance at 100 nm (A,...) 3. The ratio (A, _uu „A,„,) of both is 0.78, and according to this liquid composition, light in the near infrared region is cut evenly (absorbs well). be able to.

Example 10>

1.7 g of an equimolar mixture of the specific phosphoric acid group-containing compound represented by the above formula (9) and the specific phosphoric acid group-containing compound represented by the above formula (10), and copper benzoate anhydride 0.612 g of the hydrate was dissolved in 10 ml of methyl methacrylate (MMA) to prepare a phosphoric acid ester copper compound monomer solution (the liquid composition of the present invention). With respect to the obtained liquid composition, a spectral absorption spectrum (400 to 1500 nm) having an optical path length of 1 mm was measured. The results are shown in FIG.

In the spectral absorption spectrum shown in FIG. 10, the maximum absorbance is 0.49 (828 ηm), and the liquid composition obtained in Example 10 is in the near infrared region (800 to 1800). It can be understood that the light of (0000 nm) is efficiently absorbed.

Further, in the spectral absorption scan Bae click Bokuru shown in FIG. 1 0, 8 0 0 absorbance at nm (A ₈ a «) Chikaraku 0.4 8, 1 0 0 0 absorbance at nm (A, .. _u) is 0.36, the ratio of the two (A,. „. A _{S 1) U} ) is 0.75, and according to this liquid composition, the near infrared Light in the line region can be cut evenly (absorbed in a well-balanced manner).

Comparative Example 1>

By dissolving 0.10 g of di-2-ethylhexyl phosphate and 0.0306 g of copper benzoate anhydride in 10 ml of methyl methacrylate (MMA), A monomer solution of the acid ester copper compound (a liquid composition for comparison) was prepared.

For the obtained liquid composition, a spectral absorption spectrum (400 to 1500 nm) having an optical path length of 10 mm was measured. The results are shown in FIG.

In the spectral absorption spectrum shown in FIG. 11, the maximum absorbance is 0.38 (754 ηm), and the liquid composition obtained in Comparative Example 1 is in the near infrared region (800 to 100). It can be understood that the light of (0. 0 nm) is absorbed to some extent.

In the spectral absorption spectrum shown in FIG. 11, the absorbance (A.) at 800 nm <0.37, and the absorbance (A, _(1. ) at ₁₀₀ nm) are 0. . 1 8, the ratio of the two's _{_{(a, u a s 0;}} :..) is the 0.4 9, depending on the liquid composition may equally cut Tosuru (balance light in the near infrared region Can not be absorbed)-Example 1 1>

Acrylic coating agent “LR-2 515” (manufactured by Mitsubishi Rayon Co., Ltd., solids formed: about 50% by weight) The present invention obtained in Example 1 in 100 g in 100 g was used. The coating agent of the present invention was prepared by adding and dissolving 5 g of the above-mentioned copper phosphate ester compound. The coating agent obtained was applied to the surface of a glass plate (thickness: 1.0 mm) and dried to form a 0.5 mm-thick coat layer (near-infrared absorbing layer). An infrared absorbing plate was manufactured.

The spectral transmission spectrum (250 to 120 nm) of the obtained near-infrared absorbing plate was measured. The results are shown in Figure 12:

As shown in FIG. 12, the near-infrared absorbing plate obtained in Example 11 was able to efficiently absorb light in the near-infrared ray region (800 to 100 nm). Understood

To 95 g of methyl methyl acrylate, the phosphoric ester of the present invention obtained in Example 3 was added. A monomer composition of the present invention was prepared by adding and dissolving 5 g of a copper compound. The obtained monomer composition was placed in a glass cell having a gap of 3 mm to produce a near-infrared absorbing member of the present invention (a glass cell containing the monomer composition of the present invention).

The spectral transmission spectrum (250 to 1200 nm) of the obtained near-infrared absorbing member was measured, and the result is shown in FIG.

As shown in FIG. 13, it can be understood that the near-infrared absorbing member obtained in Example 12 efficiently absorbs light in the near infrared region (800 to 100 nm). Is performed.

5 g of the phosphoric acid ester copper compound of the present invention obtained in Example 3 was added to a solution of a base material for forming an intermediate layer obtained by dissolving 10 g of polyvinyl butyral in 100 g of toluene. By dissolving, the pressure-sensitive adhesive of the present invention was prepared.

The obtained adhesive is applied to the surface of a glass plate (1.0 mm thick), dried at 50 ° C. for 24 hours to remove toluene, and a near infrared absorbing layer (O mm thick) is formed. (Intermediate layer). Then, a glass plate (thickness: 1.0 mm) is placed on the near-infrared absorbing layer to form a near-infrared absorbing plate of the present invention (a composite glass having an intermediate layer formed from the pressure-sensitive adhesive of the present invention). Board) was manufactured.

The spectral transmission spectrum (250 to 1200 nm) of the obtained near-infrared absorbing plate was measured. The results are shown in FIG.

As shown in FIG. 14, the near-infrared absorbing plate obtained in Example 13 was able to efficiently absorb light in the near-infrared ray region (800 to 100 nm). Understood

12.8 parts of a specific phosphoric acid group-containing compound represented by the following formula (13) and 18 parts of a specific phosphoric acid group-containing compound represented by the following formula (14): A mixed monomer was prepared by sufficiently mixing 79.5 parts of methyl methacrylate (MMA) and 0.5 part of methyl styrene (a-MeSt).

To this mixed monomer, 6.0 parts of copper benzoate anhydride (metal mixed 1 formula

0 Add 0 parts of H (the content of copper ions is 1.25 parts) and stir and mix to dissolve copper benzoate in the mixed monomer. Preparation of product (A) c

Equation (1 3)

H ₂ C =

H ₂ C = C-CH _;

C ₅ H ₁₀ -COC ₂ H ₄ 1 0— C

II II

〇〇

To the monomer composition (A) prepared as described above, 2.0 parts of t-butyl peroxynedecaneate (R-ND) was added, and the composition was added to a thickness of 2 mm. And heated at 45 ° C for 7 hours, then heated from 45 ° C to 65 ° C in 4 hours, then from 65 ° C to 100 ° C in 2 hours. The temperature was raised, and the mixture was heated at 100 ° C. for 1 hour to perform cast polymerization, so that a 2 mm-thick optical filter made of a phosphate group-containing copolymer holding copper ions was obtained. An optical filter comprising the resin composition of the present invention was obtained.

The specific gravity of this optical filter was as low as I.25I, and the refractive index was I.501. The water absorption of this optical filter was measured as follows. From: (g) and mass after immersion w ₂ (g.), Dried for 5 hours an optical filter one 8 0 ° C, 2 5 ° C water was immersed for 24 hours in the weight before immersion The water absorption W (%) was determined by the following equation. As a result, the water absorption of this optical filter was 0 9 8 mass? . No devitrification after immersion was observed.

Formula :) W = w ₂ -w,) w, 100 (° 6) Example 15>

11.78 parts of a specific phosphoric acid group-containing compound represented by the following formula (15) and 8.22 parts of a specific phosphoric acid group-containing compound represented by the following formula (16) A mixed monomer was prepared by sufficiently mixing 79.5 parts of methyl methacrylate and 0.5 part of α-methylstyrene.

To this mixed monomer, 6.0 parts of copper benzoate anhydride (the content of copper ion relative to 100 parts of the mixed monomer is 1.25 parts) was added as a metal compound, and the mixture was stirred and mixed. Then, copper benzoate was dissolved in the mixed monomer to prepare a monomer composition (Α). After adding 2.0 parts of t-butyl peroxyneodecane (R-ND) to the monomer composition (Α) prepared as described above, the same procedure as in Example 14 was repeated. By performing the mold mounting, a 2 mm-thick optical filter (an optical filter composed of the resin composition of the present invention) made of a phosphoric acid group-containing copolymer holding copper ions was obtained.

Equation (15)

Equation (1 6)

The specific gravity of this optical filter was as low as 1.249, the refractive index was 1.509, and the water absorption was 0.90% by weight measured in the same manner as in Example 14. No later devitrification was observed.

0 parts of a specific phosphoric acid group-containing compound represented by the following formula (17), 3.0 parts of a specific phosphoric acid group-containing compound represented by the following formula (18), and methyl methacrylate 60.0 parts, 1,6—hexanediol methyl acrylate 20.0 parts, and fenoki methylmethacrylate 10.0 parts are mixed thoroughly. A monomer was prepared.

To this mixed monomer was added 5.0 parts of copper benzoate anhydride ('the content of copper ion was 1.0 part relative to 100 parts of the mixed monomer) as a metal compound, and the mixture was stirred and mixed. Then, copper benzoate was dissolved in the mixed monomer to prepare a monomer composition (A). The monomer composition (: A) prepared as described above was added to t-butylperoxyneode. After adding 2.0 parts of a force plate (R-ND), the mixture was poured into a mold having a thickness of 1 mm, and cast polymerization was carried out in the same manner as in Example 14 to obtain a copper ion-retaining resin. An optical filter having a thickness of 1 mm comprising an acid group-containing copolymer (an optical filter comprising the resin composition of the present invention) was obtained.

Equation (1 7)

H ₂ C = C-CH _: CH-0 CH: H ₂ C = C-CH _:

II

C〇 (CH ₂ CHO) P (〇CHCH ₂ ) 0— C II II

0 O op = H 0

o

Equation (18) H

H ₂ C = C-CH ₃ CH ₃

! I

C -〇 (CH ₂ CHO)

0 OH

The specific gravity of this optical filter was as low as 1.25, the refractive index was 1.501, and the water absorption was 1.10% by weight, which was measured in the same manner as in Example 14. Toru was not recognized

Example 1 7>

A specific monomer represented by the above formula (7) is added to a mixed monomer (monomer component) consisting of 79.5 parts of methyl methacrylate and 0.5 part of methyl styrene. Group-containing compound 12.42 parts and 7.58 parts of the specific phosphoric acid group-containing compound represented by the above formula (8) are added and mixed, and benzoic anhydride as a metal compound is added thereto. 6.0 parts of copper (the content of copper ion was 1.25 parts based on 100 parts of the total amount of the mixed monomer and the phosphoric acid group-containing compound) was added, and the mixture was stirred and mixed to obtain anhydrous benzoic acid. Copper oxide was dissolved in the mixed monomer to prepare a monomer composition (B).

To the monomer composition (B) prepared as described above, 2.0 parts of t-butylperoxynedecaneate (R-ND) was added, and then the same procedure as in Example 14 was performed. Type By performing the polymerization, a 2 mm-thick optical filter (resin composition of the present invention) consisting of an acrylic copolymer (copolymer holding copper ions via a phosphoric acid group-containing compound) is obtained. Optical filter).

The specific gravity of this optical filter is as small as 1.244, the refractive index is 1.497, and the water absorption measured in the same manner as in Example 14 is 1.02 weight? and no devitrification after immersion was observed.

(1) Optical characteristics (near infrared power cut function)

For each of the optical filters obtained in Examples 14 to 17, the spectral transmittance from the ultraviolet region to the infrared region (wavelength: 250 to 1200 nm) was measured. The results are shown in Table 1 below.

〔table 1〕

As shown in Table 1, it can be understood that the optical filter obtained in Example 14 17 efficiently absorbs light in the near infrared region (800 100 nm). . The optical filter obtained in Example 14 17 has a ratio of the light transmittance at 100 Qnm to the light transmittance at 800 nm (T,..., T „) of 1. It is understood that light in the near-infrared region can be cut evenly (can be well-balanced). The invention's effect

According to the phosphoric acid ester copper compound of the present invention, light in the near infrared region (800 000 nm) can be efficiently cut. ADVANTAGE OF THE INVENTION According to the powdery substance of this invention, the light of near-infrared region can be efficiently cut, and the dispersibility or solubility with respect to a medium is good, and with such a medium, or alone, Can be used in a wide range of fields.

According to the liquid substance of the present invention, light in the near infrared region can be efficiently cut, and the dispersibility or solubility (compatibility) with a medium is good. Alternatively, it can be used alone in a wide range of fields.

According to the paste-like substance of the present invention, light in the near-infrared region can be efficiently cut, has good dispersibility or solubility (compatibility) with a medium, and together with such a medium, Alternatively, it can be used alone in a wide range of fields.

According to the composition of the present invention, light in the near infrared region can be efficiently cut. The composition of the present invention has various properties such as liquid and paste, and can be used in all fields where near infrared absorption is required.

According to the polymer composition of the present invention, light in the near-infrared region can be efficiently and well absorbed.

ADVANTAGE OF THE INVENTION According to the monomer composition of this invention, the polymer composition which can absorb light of near-infrared region efficiently and with good balance can be comprised.

According to the resin composition of the present invention, light in the near infrared region can be absorbed efficiently and in a well-balanced manner.

In addition, the resin composition of the present invention is sufficiently lightweight, has excellent visible light transmittance, has low hygroscopicity, does not devitrify with time, and further has molding, cutting, polishing, etc. Is easy to process and excellent in productivity.

According to the coating agent of the present invention, it is possible to form a coating film (near-infrared absorbing layer) that can efficiently and uniformly cut near-infrared light.

According to the adhesive and pressure-sensitive adhesive of the present invention, it is possible to form an intermediate layer (near-infrared absorbing layer) that can efficiently and evenly emit near-infrared light.

According to the near-infrared absorbing film, near-infrared absorbing plate, and near-infrared absorbing member (cell) of the present invention, light in the near-infrared region can be efficiently and uniformly cut. (12) According to the optical filter of the present invention, light in the near-infrared region is efficiently and evenly cut. It can be suitably used as a visibility correction filter, a noise cut filter, and a heat ray absorption filter.

According to the optical fiber of the present invention, since heat rays (near infrared rays) are hardly contained in the light guided and radiated by the optical fiber, the temperature rise near the light radiating portion (in the device / in the room) is reduced. Can be suppressed.

ADVANTAGE OF THE INVENTION According to the spectacle lens of this invention, an eye can be protected from heat rays and near-infrared rays which are a cause of cataract development.

ADVANTAGE OF THE INVENTION According to the camera of this invention, the light which injects into a light receiving element can be substantially limited to the light of a visible region, and accurate photometry (exposure operation) can be performed.

According to the image input device (imaging device) of the present invention, the light incident on the imaging device (CCD, CMOS image sensor / artificial retina) can be substantially limited to light in the visible region. Photometry (exposure operation) can be performed, and the reproducibility of red components is also excellent.

ADVANTAGE OF THE INVENTION According to the infrared communication environment improvement apparatus of this invention, the noise during communication can be prevented reliably.

According to the plasma display device of the present invention, a malfunction of the remote controller due to near infrared rays does not occur around the device.

ADVANTAGE OF THE INVENTION According to the heat ray absorption filter of this invention, the temperature rise in a room etc. can be suppressed reliably.

Claims

The scope of the claims

[1] A phosphoric acid copper compound obtained by reacting a compound represented by the following formula (I) with a copper ion supplying compound. Formula (I): P〇 (OH) _n X, _-n

[However, X is

X ¹ -C-0- X ² -0- or X '— 0— C-X ² — 0--

II II

0 cO H 〇

And n is i or 2. ]

[2] A phosphate copper compound obtained by reacting a compound represented by the following formula (下記) with a copper ion-supplying compound Formula (Π): P 0 (OH) „R,-„

[However, R is

R 0 R ²⁰ 10

R ¹ ten - C or

II

0

R '— C-1 0 + R ^{: i} 0 R ² 0

II

0

R represents an alkylene group. p and q are integers of 1 to 5, respectively. ) And n is 1 or 2. ]

3) Near-infrared light comprising the phosphoric acid ester copper compound according to claim 1 or 2. X-ray absorbing powdery substance.

[4] A liquid material having a near-infrared ray absorbing property, comprising the phosphoric acid ester copper compound according to claim 1 or 2.

[5] A near-infrared ray-absorbing paste-like substance comprising the phosphoric acid ester copper compound according to claim 1 or 2.

[6] A near-infrared absorbing composition comprising at least one selected from the group consisting of the phosphoric acid ester copper compound according to claim 1 and the phosphoric acid ester copper compound according to claim 2.

[7] The composition according to claim 6, which is a liquid.

[8] The composition according to claim 6, which is in a paste form.

[9] The composition according to claim 6, comprising a monomer.

[10] The composition according to claim 6, comprising a polymer.

[11] A coating agent comprising the composition according to claim 6.

[12] An adhesive comprising the composition according to claim 6,.

13) An adhesive comprising the composition according to claim 6.

[14] A near-infrared absorbing film formed by forming a near-infrared absorbing layer comprising the powdery substance according to claim 3 on the surface of a film substrate.

[15] A near-infrared absorbing film formed by forming a near-infrared absorbing layer comprising the liquid substance according to claim 4 on a surface of a film substrate.

[16] A near-infrared absorbing film obtained by forming a near-infrared absorbing layer comprising the paste-like substance according to claim 5 on the surface of a film substrate.

[17] A near-infrared absorbing film comprising the composition according to claim 6.

[18] A near-infrared absorbing film obtained by applying the coating composition according to claim 11 to the surface of a film substrate.

[193] A near-infrared absorbing film comprising a composite film having an intermediate layer formed from the adhesive according to claim 12.

[20] A near-infrared absorbing film comprising a composite film having an intermediate layer formed from the pressure-sensitive adhesive according to claim 13. [21] A near-infrared absorbing plate comprising a near-infrared absorbing layer comprising the powdery substance according to claim 3 formed on a surface of a substrate.

[22] A near-infrared absorbing plate comprising a near-infrared absorbing layer comprising the liquid substance according to claim 4 formed on a surface of a substrate.

(23) A near-infrared absorbing plate formed by forming a near-infrared absorbing layer comprising the paste-like substance according to claim 5 on the surface of a substrate.

[24] A near-infrared absorbing plate comprising the composition according to claim 6.

[25] A near-infrared absorbing plate obtained by applying the coating composition according to claim 11 to the surface of a substrate.

[26] A near-infrared absorbing plate comprising a composite plate having an intermediate layer formed from the adhesive according to claim 12.

[27] A near-infrared absorbing plate comprising a composite plate having an intermediate layer formed from the pressure-sensitive adhesive according to claim 13.

[28] A near-infrared absorbing member in which the powdered substance according to claim 3 is contained in a cell [29] A near-infrared absorbing member in which the liquid substance according to claim 4 is contained in a cell. [30] A near-infrared absorbing member containing the paste-like substance according to claim 5 in a cell.

[31] A near-infrared absorbing member in which the liquid composition according to claim 7 is accommodated in a cell. [32] A near-infrared absorbing member in which the paste-like composition according to claim 8 is accommodated in a cell.

[33] An optical filter obtained from the phosphate copper compound according to claim 1 or 2.

[34] An optical filter obtained from the composition according to claim 6.

[35] A visibility correction filter obtained from the composition according to claim 6.

[36] A noise cut filter obtained from the composition according to claim 6.

[37] A heat ray absorbing filter obtained from the composition according to claim 6.

[38] An optical fiber obtained from the composition according to claim 6.

[39] A spectacle lens obtained from the composition according to claim 6. [40] A plasma display device in which the optical filter according to claim 34 is disposed on a front surface of the panel.

[41] An optical fiber device in which the optical filter according to claim 34 is provided in a lighting part.

[42] A camera equipped with the visibility correction filter according to claim 35.

[43] A CCD camera equipped with the visibility correction filter according to claim 35. [44] A CMOS image sensor equipped with the visibility correction filter according to claim 35.

[45] An artificial retina on which the visibility correction filter according to claim 35 is mounted.

[46] An image input device equipped with the CCD camera according to claim 43.

[47] An image input device equipped with the CMOS image sensor according to claim 44. [48] An image input device equipped with the artificial retina according to claim 45.

[49] An infrared communication environment maintenance device equipped with the noise cut filter according to claim 36.

[50] A window material comprising the heat ray absorbing filter according to claim 37.

[51] A resin composition comprising a polymer and a phosphoric acid group derived from the compound represented by the formula (I) according to claim 1, and a metal ion.

[52] It is determined that a phosphoric acid group derived from the compound represented by the formula (II) according to claim 2 and a metal ion containing copper ion as a main component are contained in the polymer. Characteristic resin composition.