JPH0873732A - Production of near-infrared absorptive urethane resin - Google Patents

Abstract

PURPOSE: To obtain a near-infrared absorptive urethane resin which effectively absorbs a light of 1,000-1,100nm in wavelength by mixing and polymerizing a specified isocyanate compound, a specified active hydrogen compound and a near-infrared absorber. CONSTITUTION: This resin is produced by polymerizing a mixture of at least one ester compound (A) selected from among isocyanates, isothiocyanates and isothiocyanato-containing isocyanates, at least one active hydrogen compound (B) selected from among polyols, polythiols and hydroxylated mercapto compounds, and a near-infrared absorber (C) represented by formula I [R1 to R10 ' are each independently H, alkyl, aryl, alkoky, etc.; M is a transition metal atom, an alkali (alkaline earth) metal atom, etc.; and at least one of R1 to R10 and at least one of R1 ' to R10 ' have each a structure of formula II (R and R' are as defined in formula I)].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a near infrared absorbing urethane resin. More specifically, in recent years, a technique utilizing near-infrared light has attracted attention, and industrial applications of near-infrared light include energy conversion materials, recording materials utilizing laser light, printing and photographic materials, and lasers. Precision processing using light, electronic equipment control system,
Used to block heat rays from sunlight. Therefore, a resin that blocks or absorbs near-infrared light from outside is required. The present invention relates to a method for producing a near infrared absorbing urethane resin used in this field.

[0002]

2. Description of the Related Art As a near-infrared absorbing urethane resin used for the above-mentioned applications, the inventors of the present invention have previously disclosed Japanese Patent Laid-Open No.
No. 4-11153 has been disclosed.

[0003]

However, Japanese Unexamined Patent Application Publication No. Sho 6
The near-infrared absorbing urethane resin disclosed in No. 4-11153 has an absorption wavelength of 650 to 900 nm, and does not effectively absorb light having a longer wavelength, that is, 1000 to 1100 nm. Therefore, 1000 ~
A near-infrared absorbing urethane resin that effectively absorbs light of 1100 nm has been desired. The present invention is 1000-11
It is an object of the present invention to provide a near infrared ray absorbing urethane resin that effectively absorbs light of 00 nm.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when a specific near-infrared absorber of the present invention is added to a urethane resin raw material and polymerized, Even though the near-infrared absorber is a dithio metal complex, the polymerization reaction can be performed without inhibiting the reaction between the ester compound of the resin component of the present invention and the active hydrogen compound, and without decomposing the near-infrared absorber. Go on, 1000 ~
It has an absorption in the wavelength range of 1100 nm and is 1000-110.
The present invention has been found to provide a resin that effectively absorbs 0 nm light.

That is, the present invention relates to a group consisting of at least one ester compound selected from the group consisting of polyisocyanate compounds, polyisothiocyanate compounds and isocyanate compounds having an isothiocyanato group, and a group consisting of a polyol, a polythiol and a mercapto compound having a hydroxyl group. A method for producing a near-infrared absorbing urethane resin, which comprises mixing at least one active hydrogen compound selected from the above and a specific near-infrared absorbing agent represented by the general formula (1) and then polymerizing the mixture. The near-infrared absorber represented by the general formula (1) used in the present invention is specifically

[0006]

Embedded image

[Wherein R _{1 to} R ′ ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono or Dialkylamino group,
It represents a mono- or diarylamino group, and each group may be cyclic by a linking group. Further, M represents a transition metal atom and its derivative or an alkali metal atom, an alkaline earth metal atom, a group III and IV group atom and its derivative. Furthermore, at least one of R _{1 to} R ₁₀ has the structure of formula (2), and at least one of R ′ _{1 to} R ′ ₁₀ has the structure of formula (2). However, in the formula, R and R ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group, a mono- or diarylamino group. Represents a group. ] It is a dithio metal complex type | system | group near-infrared absorber represented by these.

[0008] Examples of the substituted or unsubstituted alkyl group represented by the formula R ₁ to R _'10 is methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group,
iso-butyl group, sec-butyl group, t-butyl group,
n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethylpropyl group, n-hexyl group,
cyclo-hexyl group, 1,3-dimethylbutyl group,
1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1
-Ethyl-3-methylbutyl group, n-octyl group, 2-
Ethylhexyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-
a linear or branched alkyl group having 1 to 20 carbon atoms such as t-butyl-2-methylpropyl group, n-nonyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group. , Γ-methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group, and other alkoxyalkyl groups, alkoxyalkoxyalkyl groups , Alkoxyalkoxyalkoxyalkyl group, chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 2,2,2-
Halogenated alkyl groups such as trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, alkylaminoalkyl groups, dialkylaminoalkyl groups, alkoxycarbonylalkyl groups, alkylaminocarbonylalkyl Represents a group, an alkoxysulfonylalkyl group, an alkylsulfonyl group and the like.

Examples of the substituted or unsubstituted alkoxy group are methoxy group, ethoxy group, n-propyloxy group,
iso-propyloxy group, n-butyloxy group, is
o-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, 1,2-dimethyl-propyloxy group, n-hexyloxy group, cy
clo-hexyloxy group, 1,3-dimethyl-butyloxy group, 1-iso-propylpropyloxy group,
1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-
1-iso-propylpropyloxy group, 1-ethyl-
3-methylbutyloxy group, n-octyloxy group, 2
-Ethylhexyloxy group, 3-methyl-1-iso-
Propylbutyloxy group, 2-methyl-1-iso-propyloxy group, 1-t-butyl-2-methylpropyloxy group, n-nonyloxy group, etc., straight-chain or branched alkoxy group having 1 to 20 carbon atoms. , Methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, γ-methoxypropyloxy group, γ-ethoxypropyloxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, dimethoxymethoxy group, di Alkoxyalkoxy groups such as ethoxymethoxy group, dimethoxyethoxy group and diethoxyethoxy group, alkoxyalkoxyalkoxy groups such as methoxyethoxyethoxy group, ethoxyethoxyethoxy group and butyloxyethoxyethoxy group, alkoxyalkoxyalkoxy groups Lucoxy group, chloromethoxy group,
2,2,2-trichloroethoxy group, trifluoromethoxy group, 2,2,2-trichloroethoxy group, 1,
Examples thereof include halogenated alkoxy groups such as 1,1,3,3,3-hexafluoro-2-propyloxy group, alkylaminoalkoxy groups such as dimethylaminoethoxy group and diethylaminoethoxy group, and dialkylaminoalkoxy groups.

Examples of the substituted or unsubstituted aryl group include halogenated phenyl groups such as phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, fluorinated phenyl group and iodinated phenyl group, tolyl group, xylyl group, Examples thereof include a mesityl group, an ethylphenyl group, a methoxyphenyl group, an ethoxyphenyl group and a pyridyl group.

Examples of the substituted or unsubstituted aryloxy group include phenoxy group, tolyloxy group, methoxyphenyloxy group, chlorophenyloxy group, medityloxy group, naphthoxy group, alkylphenoxy group and the like.

Examples of the substituted or unsubstituted alkylthio group are methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group and is.
o-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-dimethyl-propylthio group, n-hexylthio group, cyclo-hexylthio group, 1 , 3-dimethyl-butylthio group, 1-is
o-propylpropylthio group, 1,2-dimethylbutylthio group, n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl-1-iso-propylpropylthio group, 1-ethyl-3-methyl Butylthio group, n-octylthio group, 2-ethylhexylthio group, 3-methyl-1-iso-propylbutylthio group, 2-methyl-1
A carbon number of 1-iso-propylthio group, 1-t-butyl-2-methylpropylthio group, n-nonylthio group, etc.
20 linear or branched alkylthio groups, methoxymethylthio groups, methoxyethylthio groups, ethoxyethylthio groups, propoxyethylthio groups, butoxyethylthio groups,
Alkoxyalkylthio groups such as γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, dimethoxymethylthio group, diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group , Alkoxyalkoxyalkylthio group, alkoxyalkoxyalkoxyalkylthio group, chloromethylthio group, 2,2
2, -trichloroethylthio group, trifluoromethylthio group, 2,2,2-trichloroethylthio group, 1,
Examples include halogenated alkylthio groups such as 1,1,3,3,3-hexafluoro-2-propylthio group, alkylaminoalkylthio groups such as dimethylaminoethylthio group and diethylaminoethylthio group, and dialkylaminoalkylthio groups. .

Examples of the substituted or unsubstituted arylthio group include phenylthio group, tolylthio group, chlorophenylthio group, methoxyphenylthio group, mesitylthio group, naphthylthio group, alkylphenylthio group and the like.

Examples of the substituted or unsubstituted mono- or dialkylamino group are methylamino group, dimethylamino group, ethylamino group, diethylamino group, methylethylamino group, propylamino group, dipropylamino group and butylamino group. , A dibutylamino group, a β-hydroxyethylamino group, a di- (β-hydroxyethyl) amino group,
Etc.

Examples of the substituted or unsubstituted mono- or diarylamino group include phenylamino group, diphenylamino group, tolylamino group, ditolylamino group, chlorophenylamino group and methoxyphenylamino group. As a substituent when each group may be cyclic by a linking group,

[0016]

[Chemical 3]

[In the above formula, R represents a substituted or unsubstituted alkyl group or a hydrogen atom, and Y and Y'Y "are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group and an aryloxy group, respectively. And the like.] And the like.

The atoms represented by M include Li, Na,
K, Rb, Cs, Be, Mg, Ca, Sr, R-Al,
X-Al, R-Ga, X-Ga, In-R, In-X,
R ₂ Si, X ₂ Si, R ₂ Ge, X ₂ Ge, R ₂ Sn, X ₂ S
n, Pb, Mn, Fe, Co, Ni, Co-X, Cu,
Zn, Ru, Rh, Pd, VO, etc. are mentioned. [However, R represents an alkyl group, an aryl group, or an alkoxy group, and X represents F, Cl, Br, I, CN, or SCN. ]

The addition amount of the specific near-infrared absorbing agent of the present invention varies depending on the type of the absorbing agent, the combination of monomers and other additives, but it is generally 10 ppm or more with respect to the total amount of the raw material composition. If the addition amount is less than 10 ppm, sufficient absorption capacity may not be obtained, which is not preferable.

Examples of the polyisocyanate compound used in the present invention include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate,
2,2,4-Trimethylhexane methylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate , 1,3,6-hexamethylene triisocyanate,
1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω′-diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate,
2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanato) Propyl) benzene, α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl)
Naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylene triisocyanate, aliphatic polyisocyanates such as 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane , Dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diamic acid diisocyanate, 2-isocyanatomethyl- 3- (3
-Isocyanatopropyl) -5-isocyanatomethyl-
Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane,
2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,2
1] -heptane, 2-isocyanatomethyl-2- (3-
Isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-
Isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3 Alicyclic polyisocyanate such as -isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, norbornane bis (isocyanatomethyl), phenylenediisocyanate, tolylene diisocyanate,
Ethyl phenylene diisocyanate, isopropylene phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate , 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4 '
-Diisocyanate, bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-
Diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-
Triisocyanate, 4-methyl-diphenylmethane-
3,5,2 ′, 4 ′, 6′-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylethylisocyanate, tetrahydronaphthylenediisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane-4,
Aromatic polyisocyanates such as 4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, thio Diethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, dicyclohexyl diisocyanate Sulfur-containing aliphatic isocyanate such as xyl sulfide-4,4'-diisocyanate, diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3 '
-Dimethoxy-4,4'-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene)
Sulfide, aromatic sulfide isocyanate such as 4,4′-methoxybenzenethioethylene glycol-3,3′-diisocyanate, diphenyldisulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyldisulfide-5,5 ′ -Diisocyanate,
3,3'-Dimethyldiphenyldisulfide-5,5 '
-Diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4,4'-
Aromatic disulfide-based isocyanates such as dimethyldiphenyldisulfide-5,5′-diisocyanate, 3,3′-dimethoxydiphenyldisulfide-4,4′-diisocyanate, 4,4′-dimethoxydiphenyldisulfide-3,3′-diisocyanate, Diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylmethanesulfone-2,4 '-Diisocyanate, 4,4'-dimethoxydiphenyl sulfone-
3,3'-diisocyanate, 3,3'-dimethoxy-
4,4'-diisocyanate dibenzyl sulfone, 4,
4'-Dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-
Aromatic sulfone-based isocyanates such as methoxybenzene ethylenedisulfone-3,3'-diisocyanate and 4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanate Sulfonic acid ester-based isocyanates such as natophenol ester and 4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester, 4-methyl-3-isocyanatobenzenesulfonylanilide-3′-methyl-4′- Isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4 '
-Methoxybenzenesulfonyl-ethylenediamine-
3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3 ′
-Aromatic sulfonic acid amides such as isocyanate, thiophene-2,5-diisocyanate, thiophene-2,
5-diisocyanatomethyl, 1,4-dithiane-2,5
-Sulfur-containing heterocyclic compounds such as diisocyanate and 1,4-dithian-2,5-diisocyanatomethyl.

Further, halogen-substituted products such as chlorine-substituted products, bromine-substituted products, etc., alkyl-substituted products, alkoxy-substituted products,
A nitro-substituted product, a prepolymer modified product with a polyhydric alcohol, a carbodiimide modified product, a urea modified product, a buret modified product, a dimerization or trimerization reaction product and the like can also be used.

The polyisothiocyanate compound used in the present invention is a compound containing two or more -NCS groups in one molecule, and may further contain a sulfur atom in addition to the isothiocyanato group. Specifically, for example,
1,2-diisothiocyanatoethane, 1,3-isothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylene diisopropylidene diisothiocyanate, etc. Aliphatic isothiocyanates, alicyclic isothiocyanates such as cyclohexanediisothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4
-Diisothiocyanatotoluene, 2,5-diisothiocyanato-n-xylene, 4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylenebis (4
-Isothiocyanatobenzene), 1,1'-methylenebis (4-isothiocyanato-2-methylbenzene),
1,1'-methylenebis (4-isothiocyanato-3-
Methylbenzene), 1,1 ′-(1,2-ethanediyl) bis (4-isothiocyanatobenzene), 4,4 ′
-Diisothiocyanatobenzophenone, 4,4'-diisothiocyanato-3,3'-dimethylbenzophenone,
Benzanilide-3,4'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate,
Aromatic isothiocyanates such as diphenylamine-4,4'-diisothiocyanate, heterocyclic ring-containing isothiocyanates such as 2,4,6-triisothiocyanato-1,3,5-triazine, and further hexanedioyl diisothiocyanate , Nonanedioyl diisothiocyanate,
Carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2′-bipyridine) -4,4′-dicarbonyldiisothiocyanate, etc. Thiocyanate can be mentioned.

Examples of the bifunctional or higher polyisothiocyanate having at least one sulfur atom in addition to the isothiocyanato group used as a raw material in the present invention include, for example, thiobis (3-isothiocyanatopropane) and thiobis (2-
Sulfur-containing aliphatic isothiocyanates such as isothiocyanatoethane) and dithiobis (2-isothiocyanatoethane),
1-isothiocyanato-4-{(2-isothiocyanato) sulfonyl} benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothiocyanatobenzene), sulfinylbis (4-isothiocyanatobenzene), dithiobis ( 4-isothiocyanatobenzene), 4-isothiocyanato-1-{(4-isothiocyanatophenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isothiocyanato Phenyl ester,
Sulfur-containing aromatic isothiocyanates such as 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate, thiophenone-
2,5-diisothiocyanate, 1,4-dithiane-
Examples include sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate.

Furthermore, halogen substitution products such as chlorine substitution products and bromine substitution products of these polyisothiocyanates, alkyl substitution products, alkoxy substitution products, nitro substitution products, prepolymer modification products with polyhydric alcohols, and carbodiimide modification products. Body, urea modified product, buret modified product, dimerization or trimerization reaction product, etc. can also be used.

Examples of the isocyanate compound having an isothiocyanato group used as a raw material in the present invention include 1-isothiocyanato-3-isocyanatopropane, 1-isothiocyanato-5-isocyanatopentane and 1-isothiocyanato-6-isocyanato. Hexane, isothiocyanatocarbonyl isocyanate, 1-
Aliphatic or alicyclic compounds such as isothiocyanato-4-isocyanatocyclohexane, aromatic compounds such as 1-isothiocyanato-4-isocyanatobenzene, 4-methyl-3-isothiocyanato-1-isocyanatobenzene, 2-isothiocyanato- Heterocyclic compounds such as 4,5-diisocyanato-1,3,5-triazine, and further isothiocyanato such as 4-isocyanato-4′-isothiocyanatodiphenyl sulfide and 2-isocyanato-2′-isothiocyanatodiethyl disulfide. In addition to the groups, compounds containing a sulfur atom are also included.

Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, and urea-modified products of these compounds. body,
A modified burette, a dimerized or trimerized reaction product, etc. can also be used. These ester compounds may be used alone or as a mixture of two or more kinds.

Of these ester compounds, aliphatic isocyanates and alicyclic isocyanates are preferably used from the viewpoints of easy availability and stability of the near-infrared absorbing agent, and among them, hexamethylene diisocyanate and trimethylhexadiene are preferred. Methylene diisocyanate, isophorone diisocyanate, norbornane bis (isocyanatomethyl), dicyclohexylmethane diisocyanate are preferably used.

Examples of the active hydrogen compound used in the present invention include the following. Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucose. Side, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol,
Ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycerose, diglycerol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol. , Cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0,2,6] decane-
Dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,3]
1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [ 3,4] octanediol, butylcyclohexanediol, 1,
Aliphatic polyols such as 1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol , Trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2
-Hydroxyethoxy) benzene, bisphenol A-
Bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-
In addition to aromatic polyols such as bis- (2-hydroxyethyl ether), halogenated polyols such as dibromoneopentyl glycol, polymer polyols such as epoxy resin, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid Acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-
Bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, a condensation reaction product of an organic acid such as bromophthalic acid and the polyol, an addition reaction product of the polyol and an alkylene oxide such as ethylene oxide or propylene oxide, Addition reaction products of alkylene polyamines with ethylene oxide, alkylene oxides such as propylene oxide, and further bis- [4- (hydroxyethoxy)
Phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4-
(2,3-Dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis- [2-methyl-4-]
(Hydroxyethoxy) -6-butylphenyl] sulfide and compounds obtained by adding an average of 3 molecules or less of ethylene oxide and / or propylene oxide per hydroxyl group to these compounds, di- (2-hydroxyethyl)
Sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithiane-2,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (trade name bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis (6-te
Examples thereof include polyols containing a sulfur atom such as rt-butyl-3-methylphenol), 3,6-dithiaoctane-1,8-diol, and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.

Examples of polythiols include methanedithiol, 1,2-ethanedithiol, 1,1-
Propanedithiol, 1,2-propanedithiol,
1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane, 1,1-cyclohexanedithiol, 1,2-cyclohexane Dithiol, 2,2-dimethylpropane-
1,3-dithiol, 3,4-dimethoxybutane-1,
2-dithiol, 3,6-dioxaoctane-1,8-
Dimercaptan, 2-methylcyclohexane-2,3-
Dithiol, bicyclo [2,2,1] pepta-exo-
cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3- Dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-
Mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis ( Mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercapto) Acetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
-Mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane) and other aliphatic polythiols, 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,
4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethylene) (Oxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) Benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5
-Trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3- Tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2 , 4-Tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1,2,4-
Tris (mercaptoethyleneoxy) benzene, 1,
3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,
2,3,5-tetramercaptobenzene, 1,2,4
5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5
-Tetrakis (mercaptomethyl) benzene, 1,2,
4,5-tetrakis (mercaptomethyl) benzene,
1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3 , 4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,
4,5-Tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4 5-
Tetrakis (mercaptoethyleneoxy) benzene,
2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2,6-naphthalenedithiol,
2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di (p- Aromatic polythiols such as methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane , 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4
5-tribromo-1,2-dimercaptobenzene, 2,
Halogen-substituted aromatic polythiols such as chlorine-substituted compounds such as 3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and bromine-substituted compounds, and 2-methylamino-4,6-dithiol-sym- Triazine, 2-ethylamino-4,6-dithiol-sym-triazine,
2-Amino-4,6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6 -Dithiol-sym-triazine, 2-phenoxy-4,
6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine,
2-Thiobutyloxy-4,6-dithiol-sym-
A polythiol containing a heterocycle such as triazine, further 1,2-bis (mercaptomethylthio) benzene,
1,3-bis (mercaptomethylthio) benzene, 1,
4-bis (mercaptomethylthio) benzene, 1,2-
Bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2, 4-
Tris (mermercaptomethylthio) benzene, 1,
3,5-tris (mermercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethyl) Thio)
Benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2 ，
3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, etc., and their alkyl alkyls Aromatic polythiols containing sulfur atoms in addition to mercapto groups such as compounds, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio)
Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) ethane, 1,2- ( 3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2- Bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-
Tris (2-mercaptoethylthio) propane, 1,
2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3- Dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane,
Bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc., and their thioglycolic acid and mercaptopropionic acid esters, hydroxymethylsulfide bis (2-mercaptoacetate), hydroxymethylsulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3 -Mercaptopropionate), hydroxymethyl disulfide bis (2-
Mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate) ), Hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2. , 5-diolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3-
Mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester),
Dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-
Mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester) ), Dithiodipropionic acid (2,3-
Aliphatic polythiol containing sulfur atom in addition to mercapto group such as dimercaptopropyl ester), 3,4-thiophenedithiol, 2,5-dimercapto-1,3
4-thiadiazole, 2,5-dimercapto-1,4-
Examples thereof include heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as dithiane and 2,5-dimercaptomethyl-1,4-dithiane.

Examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol and 3
-Mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2 -Propanol, 2,3-dimercapto-1-propanol, 1,2
-Dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate),
Pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-
Mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene,
4-hydroxy-4′-mercaptodiphenyl sulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris ( Examples thereof include mercaptoethylthio) methane.

Further, a chlorine-substituted product or a bromine-substituted product of these active hydrogen compounds may be used.
These may be used alone or in combination of two or more.

The compounding ratio of the above ester compound and active hydrogen compound is the functional group molar ratio (NCO + NCS) / (S
H + OH) is preferably within the range of 0.5 to 3.0, and is preferably 0.
More preferably, it is within the range of 5 to 1.5. Although less than 0.5 and more than 3.0 can be achieved, the heat resistance of the obtained resin may be impaired, which may give unfavorable results.

The near-infrared absorbing resin of the present invention is made of a urethane resin as a raw material, and mainly has a urethane bond by an iso (thio) cyanato group and an active hydrogen group. , Ureya bond,
It is of course possible to include a thiourea bond or a buret bond.

For example, it is often the case that the urethane bond is further reacted with an isocyanato group, or the dithiourethane bond is further reacted with an isothiocyanato group to increase the crosslink density. In this case, the reaction rate is increased to at least 100 ° C. or higher, and a large amount of isocyanate component or isothiocyanate component is used. Alternatively, a urea bond or a biuret bond can be used by partially using an amine or the like. When using a compound other than the active hydrogen compound that reacts with the iso (thio) cyanate compound, it is necessary to pay particular attention to the coloring point.

Depending on the purpose, as in known molding methods, various internal release agents, chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, etc. The substance may be added.

In order to adjust the reaction rate to a desired value, a known reaction catalyst used in the production of polyurethane can be added appropriately.

The resin of the present invention is usually obtained by cast polymerization. Specifically, one or more near-infrared absorbing agents represented by the general formula (1) are mixed with a mixture of an ester compound and an active hydrogen compound. At that time, if necessary, a polymerization catalyst,
Various additives such as an internal release agent and an ultraviolet absorber may be added as appropriate. This mixture is defoamed by an appropriate method as needed, then poured into a mold, and usually polymerized while gradually increasing the temperature from a low temperature of about 0 to 50 ° C to a high temperature of about 100 to 180 ° C. . At this time, in order to facilitate the releasability after polymerization, the mold may be subjected to a known releasing treatment. The time required for polymerization depends on the combination of monomers,
Although it depends on the kind and amount of the additive, it is usually 2 to 48 hours.

The urethane resin according to the present invention has a surface for improving antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property or fashionability, if necessary. Physical or chemical treatments such as polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment and light control treatment can be carried out. The near-infrared absorbing resin thus obtained is 1000 to 1100n.
Since it has absorption in the wavelength range of m and effectively absorbs light of 1000 to 1100 nm, it is useful as a protective plate for a YAG laser.

Furthermore, by using the near-infrared light absorbent represented by the general formula (1) of the present invention and the naphthalocyanine, phthalocyanine and anthraquinone-based near-infrared light absorbent exemplified in JP-A-64-11153, 650-11
It is also possible to produce a near-infrared absorbing urethane resin having absorption in a wide wavelength range of 00 nm.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 100 parts of hexamethylene diisocyanate, 145 parts of pentaerythritol tetrakis (3-mercaptopropionate), and the following structural formula (A)

[0042]

[Chemical 4] After mixing 0.061 parts of the near-infrared absorber represented by and 0.12 part of dibutyltin dichloride to defoam to obtain a uniform solution, the mixture was poured into a mold mold including a mold release-treated glass mold and a gasket. . Then, from 30 ℃ to 130
It was heated and cured for 24 hours while gradually raising the temperature to 0 ° C. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. When the absorption spectrum of the obtained resin was measured with a spectrophotometer (Shimadzu UV-3100PC), it was as shown in FIG. 1 and had absorption at 1000 to 1100 nm.

Example 2 100 parts of isophorone diisocyanate, pentaerythritol tetrakis (3-mercaptopropionate) 1
10 parts, and 0.053 parts of the near-infrared absorbing agent represented by the structural formula (A) and 0.84 parts of dibutyltin dichloride were mixed, defoamed to form a uniform solution, and then subjected to mold release treatment. It was poured into a mold composed of a gasket. Next, the temperature was gradually raised from 30 ° C. to 130 ° C., and the mixture was heated and cured for 24 hours. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. The absorption wavelength of the obtained resin was 1000 to 1100 nm.

Example 3 100 parts of dicyclohexylmethane diisocyanate, 93 parts of pentaerythritol tetrakis (3-mercaptopropionate), and 0.095 part of a near-infrared absorber represented by the structural formula (A) and dibutyltin dichloride. 5
After 8 parts were mixed and defoamed to obtain a uniform solution, the solution was poured into a mold made of a mold-treated glass mold and a gasket. Next, the temperature was gradually raised from 30 ° C. to 130 ° C., and the mixture was heated and cured for 24 hours. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. The absorption wavelength of the obtained resin was 1000 to 1100 nm.

Example 4 100 parts of norbornane bis (isocyanatomethyl), 119 parts of pentaerythritol tetrakis (3-mercaptopropionate), and the following structural formula (B)

[0046]

[Chemical 5] After mixing 0.055 parts of the near-infrared absorbing agent represented by and 0.22 part of dibutyltin dichloride to defoam to obtain a uniform solution, the mixture was poured into a mold mold composed of a mold-treated glass mold and a gasket. . Then, from 30 ℃ to 130
It was heated and cured for 24 hours while gradually raising the temperature to 0 ° C. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. The absorption wavelength of the obtained resin is 1000 to 1150.
Met.

Example 5 100 parts of trimethylhexamethylene diisocyanate,
116 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.054 parts of the near-infrared absorber represented by the structural formula (B) and 0.22 parts of dibutyltin dichloride are mixed and defoamed to obtain a uniform solution. After that, it was poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Next, the temperature was gradually raised from 30 ° C. to 130 ° C., and the mixture was heated and cured for 24 hours. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. The absorption wavelength of the obtained resin was 1000 to 1150.

Example 6 100 parts of hexamethylene diisocyanate, 145 parts of pentaerythritol tetrakis (3-mercaptopropionate), and the following structural formula (C)

[0049]

[Chemical 6] After mixing 0.061 parts of the near-infrared absorber represented by and 0.12 part of dibutyltin dichloride to defoam to obtain a uniform solution, the mixture was poured into a mold mold including a mold release-treated glass mold and a gasket. . Then, from 30 ℃ to 130
It was heated and cured for 24 hours while gradually raising the temperature to 0 ° C. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. The absorption wavelength of the obtained resin was 950 to 1100.

Examples 7 to 16 100 parts of hexamethylene diisocyanate, 145 parts of pentaerythritol tetrakis (3-mercaptopropionate), and 0.061 part of the near infrared absorbers represented by the structural formulas (D) to (M). And 0.12 parts of dibutyltin dichloride were mixed and defoamed to form a uniform solution, which was then poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Next, the temperature was gradually raised from 30 ° C. to 130 ° C., and the mixture was heated and cured for 24 hours. After the completion of the polymerization, it was cooled and the polymer was taken out from the mold. The absorption wavelengths of the obtained resins are all 950 to 1100 nm.
It was near. The results are shown in Table 1.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

According to the present invention, 1000 to 1100 nm
It is possible to obtain a near-infrared absorbing urethane resin that effectively absorbs the above light.

[Brief description of drawings]

1 is an absorption spectrum of the resin obtained in Example 1. FIG.

Claims (5)

[Claims] 1. An at least one ester compound selected from the group consisting of an isocyanate compound, an isothiocyanate compound and an isocyanate compound having an isothiocyanato group, and at least one selected from the group consisting of a polyol, a polythiol and a mercapto compound having a hydroxyl group. One or more active hydrogen compounds and a compound represented by the general formula (1): [Wherein R _{1 to} R ′ ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group. Represents a mono- or diarylamino group, and each group may be cyclic by a linking group. M is a transition metal atom and its derivative or an alkali metal atom, an alkaline earth metal atom,
Represents Group III and Group IV atoms and their derivatives. Furthermore, at least one of R _{1 to} R ₁₀ has the structure of formula (2), and at least one of R ′ _{1 to} R ′ ₁₀ has the structure of formula (2). However, in the formula, R and R ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a mono- or dialkylamino group, a mono- or diarylamino group. Represents a group. ] It mixes with the near-infrared absorbing agent represented by these, and superposes | polymerizes, The manufacturing method of the near-infrared absorbing urethane resin characterized by the above-mentioned. 2. The method for producing a near infrared absorbing urethane resin according to claim 1, wherein the ester compound according to claim 1 is an aliphatic isocyanate and / or an alicyclic isocyanate compound. 3. The aliphatic isocyanate of claim 2 and / or
Alternatively, the alicyclic isocyanate compound is one or more selected from hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane bis (isocyanatomethyl), and dicyclohexylmethane diisocyanate. 2. A method for producing a near infrared ray absorbing urethane resin. 4. The method for producing a near infrared absorbing urethane resin according to claim 1, wherein the active hydrogen compound according to claim 1 is a mercapto compound having a polythiol and / or a hydroxyl group. 5. The method for producing a near infrared absorbing urethane resin according to claim 4, wherein the polythiol according to claim 4 is pentaerythritol tetrakis (3-mercaptopropionate).