WO2011074371A1

WO2011074371A1 - Near infrared ray absorbent material and process for production thereof

Info

Publication number: WO2011074371A1
Application number: PCT/JP2010/070557
Authority: WO
Inventors: 友和戸澤; 雅大藤原; 越生堀井
Original assignee: 株式会社カネカ
Priority date: 2009-12-18
Filing date: 2010-11-18
Publication date: 2011-06-23
Also published as: TW201134880A

Abstract

Disclosed is a curable resin composition which can be cured into a product having absorption over the entire wavelength range of 700 to 1100 nm and has an an average light transmittance of 20% or less at 400 to 600 nm and a rate of change in the transmittance at a wavelength of 750 nm of within ± 5% before and after the reflow test in which a procedure of maintaining the cured product at 260°C for 60 seconds and subsequently cooling the cured product to room temperature is repeated three times. Thus, it is possible to provide: a near infrared absorbent material which has large absorption in a near infrared region and undergoes substantially no change in optical properties under high temperature conditions such as those employed in a solder reflow process; and an optical material comprising the near infrared absorbent material.

Description

Near-infrared absorbing material and manufacturing method thereof

The present invention relates to a near-infrared absorbing material and a manufacturing method thereof.

Imaging optical devices such as cameras and video use silicon diode elements, complementary metal oxide semiconductors (C-MOS), charge-coupled elements (CCDs), etc. to convert optical signals into electrical signals. . Since these photoelectric conversion elements have a light sensitive region in a wide range from 300 nm to 1000 nm from the visible light region to the near infrared region, they are highly sensitive in the near infrared region, and the projected image has color blur and distortion. . Therefore, it is required to efficiently cut light in the near infrared region 700 to 1100 nm while transmitting visible light.

Conventionally, it was designed to transmit visible light that does not transmit (reflects) infrared rays or contains infrared absorbers in order to correct the photometric sensitivity of camera photometric filters and video cameras. A glass infrared cut filter composed of a dielectric multilayer film is used. However, this type of glass filter is heavy, and has a drawback that it is difficult to process such as molding and polishing in production. For example, this type of filter made of glass needs to produce a multilayer film using metal sputtering, and the process is complicated.

In order to solve such a problem, replacement with a material that is easy to mold and lightweight is progressing. For example, a resin composition in which a near-infrared absorber is blended with an alicyclic polyolefin resin described in Patent Document 1 In addition, an optical component obtained by molding a resin composition in which a near-infrared absorber is blended with an acrylic resin described in Patent Document 2 is used for an infrared cut filter. Furthermore, as shown in Patent Document 3, a means for applying a near-infrared absorbing coating to a substrate using a coating agent containing an organic near-infrared absorbing dye has been developed to facilitate the formation of a near-infrared absorbing filter. Has been.

However, in recent years, in order to reduce the manufacturing cost at the time of assembling the imaging system lens module, a case where a solder reflow process is introduced is increasing. In such a reflow process, a material that can withstand a temperature near 300 ° C. is required.

Specifically, conventional near-infrared absorbing materials made of transparent resin have insufficient heat resistance. In fact, as in Patent Document 4, there is an example in which a near-infrared absorbing compound is added to various thermoplastic resins to form a molded body. However, in the molding process of a resin having a heat history, the near-infrared absorbing compound is thermally deteriorated. However, there is nothing that can withstand practical levels.

Further, as shown in Patent Document 5, a curable coating agent having near infrared absorption properties excellent in heat resistance and light resistance has not been disclosed so far.

Furthermore, when producing near-infrared absorbing materials, there are generally limitations on the dispersibility and solubility of the near-infrared absorbing compound in the base resin, and the desired visible light transmittance, near-infrared absorptivity, and heat resistance. It was difficult to obtain a near-infrared absorbing material having

In addition, the conventional near-infrared absorbing material made of transparent resin has low reliability in long-term use, and only a limited number of members are applicable. As in Patent Document 6, a near-infrared absorbing composition for a solid-state imaging device that sufficiently absorbs light in the region of 650 to 750 nm without losing infrared absorption capability at a temperature of about 180 ° C. in the process of manufacturing the solid-state imaging device Although an example is known, for example, a curable composition and a cured product that can maintain near-infrared absorption characteristics and optical transparency at 260 ° C. close to the upper limit of the reflow temperature have not been known so far.

Japanese Published Patent Publication "Japanese Patent Laid-Open No. 2006-233096" Japanese Patent Publication “JP 2000-7871” Japanese Patent Publication “Japanese Patent Laid-Open No. 2006-137936” Japanese Patent Publication “JP 2006-241410” Japanese Patent Publication “Japanese Patent Laid-Open No. 2006-284630” Japanese Patent Publication “Japanese Patent Laid-Open No. 2006-343631”

The present invention has been made in view of the above-described problems, and its purpose is to have a large absorption in the near infrared region, and there is substantially no change in optical characteristics under high temperature conditions such as a solder reflow process. The object is to realize a near-infrared absorbing material and an optical material containing the near-infrared absorbing material.

In order to solve the above problems, the curable resin composition according to the present invention has an absorption in the entire wavelength range of 700 to 1100 nm after the cured resin composition is held at 260 ° C. for 60 seconds. Before and after the reflow test in which the operation of cooling to room temperature is repeated three times, the average light transmittance at 400 to 600 nm is 50% or more and the average transmittance at 750 to 850 nm is 20% or less in the cured resin composition. And the change rate of the transmittance at a wavelength of 750 nm is within ± 5%.

Moreover, in order to solve the said subject, the manufacturing method of the near-infrared absorption material which concerns on this invention is a manufacturing method of the said near-infrared absorption material which concerns on this invention, and a near-infrared absorptivity with respect to 100 weight part of organic solvents. A solution in which the compound (B-2) is dispersed so as to be 1 to 50 parts by weight is prepared, and the solution is mixed with the curable composition (A), the nonionic infrared absorbing compound (B-1), and It is characterized by being applied to the surface of a molded body obtained from a transparent resin composition containing

Furthermore, the curable coating agent according to the present invention is a curable coating agent comprising the curable resin composition according to the present invention in order to solve the above-mentioned problems, and as a near-infrared absorbing compound (B), composite oxidation It includes at least one selected from the group consisting of tungsten compounds, phthalocyanine compounds, and naphthalocyanine compounds, and at least one selected from the group consisting of perylene compounds and quatarylene compounds.

Moreover, in order to solve the said subject, the curable composition which concerns on this invention is a curable composition which consists of a curable resin composition which concerns on this invention,
(A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule;
(B) a hydrosilylation catalyst;
(C) a compound containing at least two SiH groups in one molecule;
(D) a near-infrared absorbing composition comprising a quatarylene compound and at least one compound selected from a phthalocyanine compound and a naphthalocyanine compound;
It is characterized by containing.

Furthermore, the optical material according to the present invention is characterized in that the near-infrared absorbing material according to the present invention is included as an infrared shielding body.

According to the present invention, a near-infrared absorbing material having a large absorption in the near-infrared region and causing substantially no change in optical characteristics under high-temperature conditions such as a solder reflow process, and an optical material including the near-infrared absorbing material Can be provided.

Hereinafter, the present invention will be described in detail.

In the curable resin composition of the present invention, the cured resin composition has absorption in the entire wavelength range of 700 to 1100 nm, and the operation of cooling to room temperature after holding at 260 ° C. for 60 seconds is repeated three times. Before and after the reflow test, the average light transmittance at 400 to 600 nm in the cured resin composition is 50% or more, the average transmittance at 750 to 850 nm is 20% or less, and the change in transmittance at a wavelength of 750 nm. The rate is within ± 5%.

That is, in other words, the near-infrared absorbing material of the present invention is an operation in which the cured resin composition has absorption in the entire wavelength range of 700 to 1100 nm and is cooled to room temperature after being held at 260 ° C. for 60 seconds. Before and after the reflow test repeated three times, the cured resin composition has an average light transmittance of 400 to 600 nm of 50% or more, an average transmittance of 750 to 850 nm of 20% or less, and a wavelength of 750 nm. The change rate of the transmittance is within ± 5%.

As the near-infrared absorbing material exhibiting the above physical properties, for example, the following near-infrared absorbing materials (I) to (III) are preferable.

A near-infrared absorbing compound (B-2) is contained on the surface of a molded product obtained from a transparent resin composition containing the curable composition (A) and a nonionic infrared absorbing compound (B-1). Near-infrared absorbing material (I) which has a layer to do.

As the near-infrared absorbing compound (B), at least one selected from the group consisting of complex tungsten oxide compounds, phthalocyanine compounds, and naphthalocyanine compounds, and at least selected from the group consisting of perylene compounds and quatarylene compounds A near-infrared absorbing material (II) obtained by applying a curable coating agent containing at least one kind to at least one surface of a transparent substrate, evaporating the solvent, and then curing.

(A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (b) a hydrosilylation catalyst, and (c) at least two SiH groups in one molecule. A near-infrared-absorbing composition comprising: a compound containing: a (d) quatarylene compound; and at least one compound selected from a phthalocyanine compound and a naphthalocyanine compound; Near-infrared absorbing material (cured product) (III) obtained by curing.

Hereinafter, each material will be described in detail.

[1. Near-infrared absorbing material (I)]
The near-infrared absorbing material (I) is formed on the surface of a molded product obtained from a transparent resin composition containing a curable composition (A) and a nonionic infrared-absorbing compound (B-1). It has a layer containing the absorbing compound (B-2).

(1-1) Curable composition (A)
As the curable composition (A), a curable acrylic composition, a curable norbornene composition, and a curable polyimide composition after considering the compatibility between the curable composition (A) and the near-infrared absorbing compound. Products, curable epoxy silicone compositions, and curable silicone compositions can be used. Hereinafter, each curable composition will be described.

(1-1-1) Curable Acrylic Composition Generally, a curable acrylic composition is often cured with light or heat, and a photocurable acrylic resin is a photocurable acrylic that is cured using light such as ultraviolet rays. Compositions are also known. Such a photocurable acrylic composition has a high curing rate and can be cured at room temperature.

(1-1-2) Curable Norbornene Composition The curable norbornene composition will be described. Generally, norbornene-based monomers are obtained by bulk polymerization of norbornene-based monomers such as dicyclopentadiene (DCP) and methyltetracyclododecene (MTD) in the presence of a metathesis catalyst system by reaction injection molding (RIM). Obtaining a polymer is a well-known technique (Japanese Published Patent Publication “JP-A 58-129003”, Japanese Published Patent Publication “JP-A 59-51911”, Japanese Published Patent Publication “JP-A Sho”. 61-179214 ", Japanese Patent Publication" JP-A 61-293208 ", etc.).

In general, in these bulk polymerizations, a reaction stock solution containing a metathesis catalyst and a norbornene-based monomer and a reaction stock solution containing a co-catalyst and a norbornene-based monomer are prepared, and after mixing both the reaction stock solutions, the metathesis polymerization is started. The polymerization is completed by reacting to the extent that the unreacted monomer does not substantially remain.

(Norbornene polymer molded product)
The thermosetting norbornene polymer that can be used in the present invention is obtained by bulk polymerization of norbornene monomers according to a conventional method.

(Norbornene monomer)
The norbornene-based monomer that can be used in the present invention may be any monomer as long as it has a norbornene ring, but if a tricyclic or higher polycyclic norbornene-based monomer is used, a polymer having a high heat distortion temperature can be obtained. Further, in order to make the ring-opening polymer to be thermosetting type, it is necessary to use at least 10% by weight, preferably 30% by weight or more of a crosslinkable monomer in all monomers.

Specific examples of norbornene monomers include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclic compounds such as tetracyclododecene, and pentacyclic compounds such as tricyclopentadiene. Heterocycles such as tetracyclopentadiene, alkyl substitutions thereof (eg, methyl, ethyl, propyl, butyl substitutions, etc.), alkenyl substitutions (eg, vinyl substitutions), alkylidene substitutions (eg, ethylidene substitutions) Etc.), aryl-substituted products (for example, phenyl, tolyl, naphthyl-substituted products, etc.), substituted products having polar groups such as ester groups, ether groups, cyano groups, and halogen atoms. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of availability, reactivity, heat resistance, and the like, it is preferable to use a tricycle or a pentacycle.

The crosslinkable monomer is a polycyclic norbornene-based monomer having two or more reactive double bonds, and specific examples thereof include dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. When the norbornene monomer and the crosslinkable monomer are the same, it is not necessary to use other crosslinkable monomers. In addition, a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, cyclododecene, or the like that can be ring-opening copolymerized with one or more of the norbornene-based monomers may be used in combination as long as the object of the present invention is not impaired. it can.

(Metathesis catalyst system)
In the present invention, a known metathesis catalyst system comprising a metathesis catalyst and an activator can be used as a catalyst for ring-opening polymerization of a norbornene monomer. Specific examples of the metathesis catalyst include halides such as tungsten, molybdenum, and tantalum, oxyhalides, oxides, and organic ammonium salts. Specific examples of the activator (cocatalyst) include alkylaluminum halides, alkoxyalkylaluminum halides, aryloxyalkylaluminum halides, and organic tin compounds.

The metathesis catalyst is usually used in an amount of about 0.01 to 50 mmol, preferably 0.1 to 20 mmol, relative to 1 mol of the norbornene monomer. The activator is preferably used in the range of 1 to 10 (molar ratio) with respect to the metathesis catalyst. The metathesis catalyst and the activator are both preferably dissolved in the monomer, but may be used by suspending or dissolving in a small amount of solvent as long as the properties of the product are not essentially impaired.

(1-1-3) Thermosetting polyimide composition Examples of the thermosetting polyimide include, but are not limited to, nadic acid type polyimides such as bismaleimide type polyimide and allyl nadiimide, and acetylene type polyimides. .

Thermosetting polyimide has the advantage that it is easier to process than thermoplastic polyimide and non-thermoplastic (aromatic) polyimide. Although the high temperature characteristics are inferior to those of non-thermoplastic polyimides, it is a very good class among various organic polymers. Moreover, since voids and cracks hardly occur during curing, it is suitable as a component of the resin composition of the present invention. The thermosetting polyimide can be obtained, for example, by using a low molecular weight monomer or oligomer having an unsaturated group at the terminal as a prepolymer, and three-dimensionally cross-linking it through an addition reaction, a condensation reaction or a radical reaction.

As the addition type thermosetting polyimide, for example, an allyl nadiimide type, a maleimide type, a triazine type, or a Michael addition type polyimide can be used. The addition type polyimide is cured by an addition reaction of unsaturated groups in the prepolymer (low molecular weight monomer or oligomer). Therefore, condensed water and other volatile substances are not generated during curing, and a composition free from bubbles and cracks is obtained.

Prepolymers of addition type polyimides include, for example, reaction of allyl nadic acid anhydride and diamine (hexamethylenediamine, bis (4-aminophenyl) methane, m-xylylenediamine, etc.), allyl nadic acid anhydride and hydroxyphenyl It can be obtained by reaction with amine or allylamine, reaction of maleic anhydride or the like with diamine (for example, diaminodiphenylmethane), reaction of vinylbenzyl compound or the like with maleimide or the like.

(1-1-4) Curable Epoxy Silicone Composition The curable epoxy silicone composition has at least one aliphatic unsaturated monovalent hydrocarbon group in one molecule as an essential component, and at least 1 Use of an organosilicon compound having at least one silicon-bonded hydroxyl group, a hydrogenated epoxy resin partially or completely hydrogenated with an aromatic epoxy resin or aromatic ring, and a resin comprising an organohydrogenpolysiloxane It is preferable. In this case, it is preferable to mix a platinum group metal catalyst and an aluminum curing catalyst, and the curing mode is preferably heat curing.

(1-1-5) Curable Silicone Composition As the curable silicone composition, conventionally known curable silicone compositions can be used. For example, addition reaction curable silicone compositions, condensation reaction curable silicone compositions, An organic peroxide curable silicone composition and an ultraviolet curable silicone composition can be mentioned, and since the handling workability thereof is easy, a condensation reaction curable silicone composition or an addition reaction curable silicone composition is preferable. In the invention, addition reaction curable silicone compositions are particularly preferred.

The addition reaction curable silicone composition used in the present invention will be described below.

Examples of the addition reaction curable silicone composition that can be preferably used include (a) an organic compound having two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and (b) hydrosilyl. And a composition containing (c) a compound having at least two SiH groups in one molecule. By using the composition, it is possible to provide a material having both molding processability and reflow resistance.

Hereinafter, the components (a), (b), and (c) will be described.

<Component (a)>
Component (a) is an organic compound containing two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule. The organic compound does not contain a siloxane unit (Si—O—Si) such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, but includes C, H, N, O, S, and halogen. It is preferable that an element selected from the group consisting of: Those containing siloxane units may cause gas permeability and repelling problems.

The bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

Component (a) organic compounds can be classified into organic polymer compounds and organic monomer compounds.

Examples of organic polymer compounds include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, poly (meth) acrylate ester, polyamide, phenol-formaldehyde (Phenol resin type) and polyimide type compounds can be used.

In particular, polyesters, polycarbonates, and poly (meth) acrylates are preferred from the viewpoint of heat resistance and transparency.

Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene; linear aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclohexane, norbornene, and adamantane; Heterocyclic compounds such as isocyanuric compounds, tetrahydropyrans and triazines, and mixtures thereof.

The carbon-carbon double bond having reactivity with the SiH group of component (a) is not particularly limited, but the following general formula (I)

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Is preferable from the viewpoint of reactivity. Moreover, from the ease of acquisition of a raw material, the group whose R < ¹ > in the said general formula (I) is a hydrogen atom is especially preferable.

As the carbon-carbon double bond having reactivity with the SiH group of component (a), an alicyclic group having a partial structure represented by the following general formula (II) in the ring is the heat resistance of the cured product. Is preferable from the viewpoint of high.

(In the formula, R ² each independently represents a hydrogen atom or a methyl group.)
In view of the availability of the raw material, an alicyclic group having a partial structure in which R ² is a hydrogen atom in the general formula (II) in the ring is preferable.

The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton of the component (a) or may be covalently bonded through a divalent or higher substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but includes only an element selected from the group consisting of C, H, N, O, S, and halogen as a constituent element. Those are preferred. Examples of these substituents include

Is mentioned. Two or more of these divalent or higher valent substituents may be connected by a covalent bond to form one divalent or higher valent substituent.

Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Oxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group, vinyl ether group,

Is mentioned.

Specific examples of the component (a) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1 , 1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl isocyanuric acid, diallyl monobenzyl isocyanurate, 1,2,4 -Trivinylcyclohexane, 1,4-butanediol divinyl ether, nonanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether , Triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1 , 3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, tetraallyl bisphenol A, 2,5-diallylphenol allyl ether, and These oligomers, 1,2-polybutadiene (the ratio of 1,2 is 10 to 100 mol%, preferably the ratio of 1,2 is 50 to 100 mol%), allyl ether of novolak phenol, allylation Polyphenylene oxide,

In addition, the glycidyl group of a conventionally known epoxy resin may be partially or entirely replaced with an allyl group or a (meth) acryloyl group.

As the component (a), a low molecular weight compound which is difficult to express separately as described above by dividing into a skeleton portion and an alkenyl group (a carbon-carbon double bond having reactivity with a SiH group) can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene; fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples include aliphatic cyclic polyene compound systems; substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

The average number of carbon-carbon double bonds reactive with the SiH group of component (a) may be at least 2 per molecule (preferably 2 to 6 per molecule). When it is desired to further improve the mechanical strength, it is preferably more than 2, more preferably 3 or more.

When the number of carbon-carbon double bonds having reactivity with the SiH group of component (a) is less than 2 per molecule, the reaction with component (c) only results in a graft structure, Don't be. On the other hand, when the number of carbon-carbon double bonds reactive with the SiH group of component (a) is more than 6 per molecule, the storage stability of the curable composition tends to deteriorate.

As the component (a), those having a molecular weight of less than 900 are preferable from the viewpoint of high mechanical heat resistance and from the viewpoint of low formability of the raw material liquid, good moldability, handleability, and coatability. Those less than 700 are more preferred, and those less than 500 are even more preferred.

In order to obtain good workability, the component (a) preferably has a viscosity at 23 ° C. of less than 100 Pa · s, more preferably less than 30 Pa · s, and still more preferably less than 3 Pa · s. . The viscosity here refers to a value measured by an E-type viscometer.

Component (a) has the following general formula (IV) from the viewpoint of high heat resistance (reflow resistance) and light resistance.

(In the formula, R ³ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least two R ³ may be SiH groups and Including a carbon-carbon double bond having the reactivity of
The compound represented by these is preferable.

R ^{3 in the} general formula (IV) is composed only of an element selected from the group consisting of C, H, O, and N from the viewpoint that the heat resistance of the obtained cured product can be further increased. An organic group is preferable, and the organic group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 4 carbon atoms. . Examples of these preferable R ³ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.

R ^{3 in the} general formula (IV) is only an element selected from the group consisting of C, H, and O as constituent elements from the viewpoint that the chemical thermal stability of the resulting cured product can be improved. It is preferably a monovalent organic group having 1 to 50 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms. Examples of these preferable R ³ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,

Etc.

As R ³ of the general formula (IV), at least one (preferably at least two) of the three R ³ is from the viewpoint of good reactivity.

It is preferably a monovalent organic group having 1 to 50 carbon atoms and containing only one element selected from the group consisting of C, H, O, and N as a constituent element. The following general formula (V)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group.)
More preferably, it is a monovalent organic group having 1 to 50 carbon atoms, which contains at least one group represented by formula (II) and contains only elements selected from the group consisting of C, H, O and N as constituent elements. At least two of the three R ³ are represented by the following general formula (VII)

(Wherein R ⁶ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group.)
More preferably, the organic group is represented by the formula (R ⁷ and R ⁶ may be different or the same).

R ^{6 in the} general formula (VII) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the obtained cured product can have higher heat resistance, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group.

R ^{6 in the} general formula (VII) is a direct bond or a group consisting of C, H, and O as constituent elements from the viewpoint that chemical thermal stability of the obtained cured product can be improved. A divalent organic group having 1 to 48 carbon atoms containing only selected elements is preferred, and preferred examples of R ⁶ include the following.

R ^{7 in the} general formula (VII) is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of good reactivity.

However, in the preferred examples of the organic compound represented by the general formula (IV) as described above, it is necessary to contain two or more carbon-carbon double bonds having reactivity with the SiH group in one molecule. is there. From the viewpoint of further improving the heat resistance, it is more preferably an organic compound containing three or more carbon-carbon double bonds having reactivity with SiH groups in one molecule.

Preferred examples of the organic compound represented by the general formula (IV) as described above include triallyl isocyanurate, diallyl monoglycidyl isocyanurate, and mixtures thereof.

Component (a) can be used singly or in combination of two or more, and in order to adjust the flexibility of the resulting cured product, an organic compound having only one carbon-carbon double bond is suitably used. You may mix.

In particular, from the viewpoint that the obtained cured product is less colored and has high light resistance, the component (a) is an aliphatic cyclic olefin compound having 6 to 50 carbon atoms having two or more vinyl groups or allyl groups, a vinyl group. Alternatively, an isocyanuric derivative having two or more allyl groups is preferable.

Specific examples of the C6-C50 aliphatic cyclic olefin compound having two or more vinyl groups or allyl groups include vinylcyclohexene, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, 1,2, Mention may be made of 4-trivinylcyclohexane.

Specific examples of the isocyanuric derivatives having two or more vinyl groups or allyl groups include triallyl isocyanurate and diallyl monoglycidyl isocyanurate. Of these, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane are particularly preferable.

Above all, from the viewpoint of high heat resistance and refractive index, the following general formula (III)

(Wherein R ⁴ represents an organic group which may be substituted with a monovalent oxygen, nitrogen, sulfur or halogen atom having 1 to 50 carbon atoms, and each R ⁴ may be different or the same. May be good.)
Of these, an organic compound having a structure represented by the formula (1) is preferable, and among them, a compound in which part or all of the glycidyl group bonded to the aromatic ring-containing epoxy resin is substituted with an allyl group is preferable.

Specifically, divinylbenzenes, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, bisphenol A diallyl ether, bis [4- (2-allyloxy) ) Phenyl] sulfone, phenol novolac resin.

In addition, as the general formula (III), from the viewpoint that the heat resistance of the obtained cured product can be higher,

It is preferable to have a plurality of aromatic rings.

<Component (b)>
Next, the hydrosilylation catalyst as component (b) will be described.

The hydrosilylation catalyst of component (b) is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; Platinum acid; complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ); Platinum-vinylsiloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) _a , Pt [(MeViSiO) ₄ ] _b ); platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ); platinum - phosphite complex _{_{(e.g., Pt [P (OPh) 3}} ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me Methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, a and b represent an integer.); Dicarbonyldichloroplatinum; a Karlstedt catalyst; a platinum-hydrocarbon complex (for example, Platinum-hydrocarbon complexes described in Ashby, US Pat. Nos. 3,159,601 and 3,159,662; platinum alcoholate catalysts (eg, in Lamoreaux, US Pat. No. 3,220,972). Mention may be made of the platinum alcoholate catalysts described.

In addition, platinum chloride-olefin complexes (eg, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946) are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. Etc.

Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.

The amount of component (b) to be added is not particularly limited, but the lower limit of the preferable amount to be added is sufficient to have sufficient curability and keep the cost of the curable composition relatively low. ^{10 -8} mol per mol, and more preferably ^{10 -6} mole, ^{10 -1} moles per mole of the SiH group in the preferred amount of upper component (c), more preferably ^{10 -2} mol is there.

In addition, a cocatalyst can be used in combination with the catalyst. Examples of the cocatalyst include a sulfur-based compound such as simple sulfur, and an amine-based compound such as triethylamine.

The addition amount of the co-catalyst is not particularly limited with respect to the hydrosilylation catalyst 1 mol, the lower limit 10 ^-2 mol, preferably in the range of the upper limit 10 ² mol, more preferably lower 10 ^-1 mol, the upper limit 10 mols It is.

<Component (c)>
Next, the component (c) will be described.

Component (c) is a compound having at least two SiH groups in one molecule, but from the viewpoint of reducing compatibility with component (a) and volatility during curing, a polyorganosiloxane compound and an organic compound Are preferably partially reacted with each other (modified). The reaction for modification is not particularly limited, and an addition reaction, a condensation reaction, a dehydrogenation reaction, and the like can be used. From the viewpoint that a side reaction is difficult to proceed and a SiH group-containing compound can be stably obtained, the following organic compounds are used. A hydrosilylation product of the compound (α) and the polyorganosiloxane compound (β) (hereinafter sometimes referred to as “modified polyorganosiloxane compound”) is preferable.

(Organic compound (α))
Hereinafter, the organic compound (α) will be described.

The organic compound (α) may be an organic compound having at least one carbon-carbon double bond having reactivity with SiH group in one molecule, and the compounds listed in the component (a) are also the same. Can be used.

In the present invention, the organic compound (α) is represented by the following general formula (IV) from the viewpoint of further improving heat resistance and light resistance.

(Wherein R ³ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ may be a SiH group and Including a carbon-carbon double bond having the reactivity of
It is preferable that it is an organic compound represented by these.

Among them, the organic compound (α) is preferably triallyl isocyanurate, diallyl monoglycidyl isocyanurate, or divinylbenzene from the viewpoint that heat resistance and light resistance can be further improved. Further, it is more preferable to use diallyl monoglycidyl isocyanurate or divinylbenzene because the degree of decrease in heat resistance and light transmittance on the long wavelength side is large.

In the present invention, from the viewpoint of improving the refractive index, styrene having one carbon-carbon double bond, α-methylstyrene, allyl glycidyl ether, vinyl dioxolane, 4-vinyl-1-cyclohexene-1,2-epoxide, Compounds such as 4-vinyl-1,3-dioxolane, N-vinylcaprolactam, N-vinylphthalamide, 1-vinylpyrrolidone, monoallyldiglycidyl isocyanurate, and the following general formula (III)

(In the formula, R ⁴ represents an organic group which may be substituted with monovalent oxygen, nitrogen, sulfur or halogen atom having 1 to 50 carbon atoms, and each R ⁴ may be different and the same. Good.)
It is preferable to use an organic compound (α) having a structure represented by:

Specifically, a compound having one or two carbon-carbon double bonds having reactivity with a SiH group is preferable, and a compound having two is particularly preferable.

Specific examples of the compound having one carbon-carbon double bond include styrene, α-methylstyrene, allyl glycidyl ether, vinyl dioxolane, 4-vinyl-1-cyclohexene-1,2-epoxide, 4-vinyl-1 , 3-dioxolane, N-vinylcaprolactam, N-vinylphthalamide, 1-vinylpyrrolidone, monoallyl diglycidyl isocyanurate and the like.

Specific examples of the compound having two carbon-carbon double bonds include divinylbenzenes, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, A glycidyl group partially or entirely bonded to an aromatic ring-containing epoxy resin such as bisphenol A diallyl ether, bis [4- (2-allyloxy) phenyl] sulfone, or phenol novolak resin is preferably used. be able to.

Further, as the organic compound (α), a compound represented by the following formula or a compound having a polycyclic aromatic hydrocarbon is used from the viewpoint that the heat resistance and refractive index of the obtained cured product can be further increased. Among them, divinylbenzenes, bis [4- (2-allyloxy) phenyl] sulfone, and divinylnaphthalene are particularly preferable from the viewpoint of availability.

The various organic compounds (α) described above may be used alone or in combination of two or more.

(Polyorganosiloxane compound (β))
Next, the polyorganosiloxane compound (β) will be described.

The polyorganosiloxane compound (β) is not particularly limited as long as it is a polyorganopolysiloxane compound having at least 3 SiH groups in one molecule. For example, one having at least 3 SiH groups in one molecule is used. Can be used. From the viewpoint of resistance to oxidation deterioration, a chain, cyclic, branched or cage polyorganosiloxane compound having at least three SiH groups in one molecule is preferable. Specific compounds are described in Japanese Patent No. 35669919.

From the viewpoint of imparting flexibility to the cured product, a chain organopolysiloxane having at least 3 SiH groups in one molecule is preferable, and in particular, at least 3 SiH groups in one molecule represented by the following formula: A linear organopolysiloxane having the following formula is preferred.

(Wherein R ⁹ , R ¹⁰ , and R ¹¹ represent an organic group having 1 to 10 carbon atoms, and may be the same or different, l is 1 to 50, m is 0 to 50, and n is 2) To 50, p represents 0 to 50, q represents 3 to 50, and r represents a number from 0 to 50.)
R ⁹ , R ¹⁰ and R ¹¹ are preferably methyl groups from the viewpoints of availability and heat resistance, and are preferably phenyl groups from the viewpoint of increasing the strength of the cured product.

A branched organopolysiloxane is preferable from the viewpoint of high heat resistance of the cured product. Among them, at least three SiH groups represented by the following formula are included in one molecule, and a T or Q structure is included in the molecule. Branched or caged organopolysiloxanes are preferred.

(In the formula, R ¹² and R ¹³ are the same or different and each represents an organic group having 1 to 10 carbon atoms, and n represents a number from 0 to 50.)
R ¹² and R ¹³ are particularly preferably methyl groups from the viewpoints of availability and heat resistance.

From the viewpoint of availability and good reactivity with the compound (α), a cyclic organopolysiloxane is preferable, and among them, at least three SiH groups are represented in one molecule represented by the following general formula (VI). Cyclic organopolysiloxane is preferred.

(Wherein R ¹⁴ and R ¹⁵ are the same or different and each represents an organic group composed of an element selected from the group consisting of C, H and O, n is 3 to 10, and m is 0 to 10) Represents the number of

The substituents R ³ and R ⁴ in the compound represented by the general formula (VI) are preferably organic groups having 1 to 10 carbon atoms, more preferably hydrocarbon groups, and methyl groups. Is more preferable. M is preferably 0.

As the compound represented by the general formula (VI), 1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability and reactivity.

The various polyorganosiloxane compounds (β) described above can be used alone or in combination of two or more.

As the catalyst for the hydrosilylation reaction between the organic compound (α) and the polyorganosiloxane compound (β), the catalysts and promoters mentioned in the component (b) can be used in the same manner.

The addition amount of the catalyst is not particularly limited, but in order to keep the cost of the curable composition relatively low, the preferred lower limit of the addition amount is 10 ⁻⁸ mol per 1 mol of SiH groups of the polyorganosiloxane compound (β), More preferably, it is 10 ⁻⁶ mol, and the upper limit of the preferable addition amount is 10 ⁻¹ mol, more preferably 10 ⁻² mol, per 1 mol of SiH groups in the polyorganosiloxane compound (β).

(Reaction between organic compound (α) and polyorganosiloxane compound (β))
The modified polyorganosiloxane compound in the present invention is a compound obtained by reacting an organic compound (α) and a polyorganosiloxane compound (compound (β) in the presence of a hydrosilylation catalyst.

There are various reaction orders and methods of the organic compound (α) and the polyorganosiloxane compound (β). From the viewpoint that it is difficult to contain a low molecular weight substance, an excess of the organic compound (α) and the polyorganosiloxane compound ( β), or an excess of the polyorganosiloxane compound (β) and the organic compound (α) are subjected to a hydrosilylation reaction, and then the unreacted organic compound (α) or the polyorganosiloxane compound (β) is temporarily removed. More preferred.

The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C, more preferably 50 ° C, and the upper limit of the preferable temperature range is 200 ° C, more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

The reaction time and the pressure during the reaction can be set as required.

Oxygen can be used in the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. The oxygen volume concentration in the gas phase is preferably 0.1% or more, more preferably 1% or more, from the viewpoint that the effect of promoting the hydrosilylation reaction by addition of oxygen is observed.

Further, a solvent may be used in the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane; tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. A solvent may be used independently and can also be used as 2 or more types of mixed solvents. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

It is also possible to remove the solvent and / or unreacted compound after the hydrosilylation reaction of the organic compound (α) and the polyorganosiloxane compound (β). By removing these volatile components, the reaction product obtained does not have volatile components. Therefore, when a cured product is produced using the reaction product, problems of voids and cracks due to volatilization of volatile components are unlikely to occur. . Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 85 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

The mixing ratio of the organic compound (α) and the polyorganosiloxane compound (β) is not particularly limited as long as two or more SiH groups remain in one molecule. Considering the strength of the cured product of the present invention, since it is preferable that the (β) component has more SiH groups, the number of moles of carbon-carbon double bonds having reactivity with SiH groups in the organic compound (α). The ratio of (A1) to the number of moles of SiH groups (B1) in the polyorganosiloxane compound (β) is preferably B1 / A1 ≧ 2, and more preferably B1 / A1 ≧ 2.5. preferable.

(1-2) Near-infrared absorbing compound In the near-infrared absorbing material (I), as a near-infrared absorbing compound, a nonionic infrared-absorbing compound (B-1) contained in the molded body and a layer on the surface of the molded body are contained. The near infrared absorbing compound (B-2).

Near-infrared rays generally represent a wavelength band of 700 to 2500 nm, but a region that needs to be cut in a light-sensitive region of an optical element represents a near-infrared wavelength band of approximately 700 to 1100 nm. The near-infrared absorbing compound of the present application is a compound having a near-infrared absorbing ability, but can cover absorption in the near-infrared region of about 700 to 1100 nm.

From the viewpoint of providing high thermal stability, that is, reflow resistance, the near-infrared absorbing compound preferably has a heat decomposition temperature of 260 ° C. or higher, preferably 300 ° C. or higher.

The near-infrared absorbing compound (B-1) is a nonionic compound. If the near-infrared absorbing compound in the molded body is an ionic compound, it will be modified or decomposed during curing of the matrix resin and will not exhibit its original absorption characteristics. There is a case.

In the near-infrared absorbing material (I), the non-ionic near-infrared absorbing compound (B-1) is preferably a quatarylene compound and a perylene-based compound, or a combination thereof. (B-2) is preferably an inorganic cesium-containing composite tungsten oxide.

The quatarylene compound and the perylene compound are preferably compounds having an absorption region band at 650 to 850 nm and a high heat resistance having a decomposition temperature of 300 ° C. or higher. For example, a compound represented by the following structural formula is used. Can be mentioned.

In the formula (VIII), two Rs may be the same or different and are independent of each other and are hydrogen, ether functional 1-4 oxygen atoms, 1-4 imino groups, or 1- An alkyl group having 1 to 20 carbon atoms, which may be interrupted by four N- (alkyl having 1 to 4 carbon atoms) imino groups, or an unsubstituted or alkyl substituted phenyl having 1 to 4 carbon atoms It is a group.

The alkyl group in formula (VIII) may be linear or branched, and the alkyl-substituted phenyl group having 1 to 4 carbon atoms generally has 1 to 3 carbon atoms having 1 to 4 carbon atoms. It may have an alkyl substituent.

As the nonionic near-infrared absorbing compound (B-1), a compound having solubility in an organic solvent, component (a) or component (c) is preferably used. When it is soluble in the organic solvent, component (a), or component (c), it becomes easy to produce the curable composition and the light transmittance in the visible light region is increased. The solubility of the nonionic near-infrared absorbing compound (B-1) in the organic solvent, component (a), or component (c) is 100% by mass of the organic solvent, component (a), or component (c). The solubility is preferably 0.001% by mass or more.

The organic solvent that can be used in the preparation of the curable composition is not particularly limited, and examples thereof include aromatic solvents such as toluene and xylene; alcohols such as iso-propyl alcohol, n-butyl alcohol, and propylene glycol methyl ether. Solvents; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; one or two of dimethylformamide and the like More than species.

In addition to the above, for example, aminothiol nickel complex compound; anthraquinone compound; thiol nickel complex compound; triarylmethane compound; naphthoquinone compound; nitroso compound and its metal complex salt; Organic substances such as carbon black, tin oxide doped with antimony oxide or indium oxide, inorganic oxides, oxides, carbides or borides of metals belonging to Group 4, 5 or 6 of the periodic table be able to. Moreover, these can be utilized according to the required heat resistance conditions, and may be used independently and may be used together 2 or more types.

Nonionic near-infrared absorbing compound (B-1): “Lumogen® IR-765” as a quartarylene compound, “Lumogen® IR-788” as a perylene compound (both trade names, manufactured by BASF), phthalocyanine compound "E-ex color IR-10", "e-ex color IR-12", "e-ex color IR-14", "e-ex color HA-1", "e-ex color HA-14" (Manufactured by Nippon Shokubai Co., Ltd.), “YKR-3070”, “YKR-3080”, “YKR-3070” (all trade names, manufactured by Yamamoto Kasei Co., Ltd.), “Lumogen® IR-5055 as an organic / inorganic nanohybrid compound (Trade name, manufactured by BASF) and the like.

When the composition containing the components (a) to (c) described above is used as the curable composition (A), the amount of the nonionic near-infrared absorbing compound (B-1) used is component (a). And it is preferable to set it as 0.0005 weight part or more with respect to 100 weight part of total amounts with a component (c), and it is preferable to set it as 20 weight part or less. More preferably, it is 0.0015 weight part or more, and 10 weight part or less, More preferably, it is 0.002 weight part or more, and 7 weight part or less. If the amount to be added is small, the cured product formed from the cured composition having near infrared absorption performance may not exhibit sufficient near infrared absorption performance, and if it is too large, the transmittance in the visible light region may decrease. Light may be scattered by aggregation.

From the viewpoint of resin dispersibility, the near-infrared absorbing compound (B-1) is preferably a phthalocyanine compound or a naphthalocyanine compound.

The phthalocyanine-based compound and naphthalocyanine-based compound exhibit an absorption region band at 800 to 1200 nm and preferably have high heat resistance. From the viewpoint of visible light transmission, a phthalocyanine-based compound is preferable. The main central metal chelated to the phthalocyanine compound is copper, but is not particularly limited thereto.

As the near-infrared absorbing compound (B-2), inorganic fine particles are preferable from the viewpoint of heat resistance.

As the inorganic fine particles, antimony-doped tin oxide (ATO) fine particles and indium tin oxide (ITO) fine particles are preferable. From the viewpoints of near infrared absorption performance and visible light transmittance, tungsten oxide which is an inorganic infrared absorber. Are preferable, and composite tungsten oxide is more preferable.

As the composite tungsten oxide, the general formula (1)
MmWOn (1)
(In the formula, M element is H, He, alkali metal, alkaline earth metal, rare earth element, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, One or more elements selected from Hf, Os, Bi, and I are shown, and m and n are numbers satisfying 0.001 ≦ m ≦ 1.0 and 2.2 ≦ n ≦ 3.0. .)
The compound represented by these can be mentioned.

The composite tungsten oxide represented by the general formula (1) has excellent durability when it has a hexagonal, tetragonal, or cubic crystal structure, and is therefore selected from the hexagonal, tetragonal, and cubic crystals. Preferably it contains more than one crystal structure. Of these, hexagonal crystals are particularly preferred because they have the least absorption in the visible light region. For example, as a composite tungsten oxide having a hexagonal crystal structure, one type selected from each element of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as preferable M elements. A composite tungsten oxide containing the above elements can be given.

The addition amount (content) m of M element in the composite tungsten oxide is preferably 0.001 or more and 1.0 or less, more preferably about 0.33. This is because the value of m theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics as an infrared absorber can be obtained with the addition amount before and after this.

On the other hand, the amount n of oxygen is preferably 2.2 or more and 3.0 or less. Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like, and m and n fall within the above ranges. If it is a thing, a useful near-infrared absorption characteristic can be acquired.

In the present invention, as the composite tungsten oxide, a cesium-containing composite tungsten oxide is preferable from the viewpoints of optical properties, weather resistance, and the like as an infrared absorber. -A)
Cs _{0.2 to 0.4} WO _{2.5 to 3.0} (1-a)
The compound represented by these can be mentioned.

The composite tungsten oxide has much better weather resistance and higher visible light transmittance than organic fluorine-containing phthalocyanine compounds, which are known to be particularly excellent in weather resistance.

The composite tungsten oxide is preferably used in the form of fine particles, and the average particle diameter is preferably 800 nm or less, and more preferably 100 nm or less, from the viewpoint of dispersibility, optical properties, and the like.

In the present invention, one type of the composite tungsten oxide may be used, or two or more types may be used in combination. The content of the composite tungsten oxide is usually 5 to 60% by mass, preferably 10 to 40% by mass, from the viewpoints of near infrared absorption performance, dispersibility, performance as a hard coat layer, and the like.

As the inorganic infrared absorber, ATO or ITO may be used, but from the viewpoint of near infrared absorption characteristics, tungsten oxide is more effective in the present invention.

In the present invention, as long as the effect of the present invention is not impaired, other inorganic infrared absorbents and organic infrared absorbents can be used in combination with the composite tungsten oxide as desired.

Other inorganic infrared absorbers include, for example, tungsten oxide compounds other than composite tungsten oxide, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, zinc oxide, indium oxide, tin-doped indium oxide (ITO), tin oxide , Antimony-doped tin oxide (ATO), cesium oxide, zinc sulfide, LaB ₆ , CeB ₆ , PrB ₆ , NdB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , HoB ₆ , YB ₆ , SmB ₆ , EuB ₆ , EuB ₆ Examples thereof include hexaboride such as ErB ₆ , TmB ₆ , YbB ₆ , LuB ₆ , SrB ₆ , CaB ₆ , (La, Ce) B ₆ .

As shown in the specification of Japanese Patent Application Publication No. 2009-114326, cesium-containing composite tungsten oxide has little absorption in the visible light region and shows absorption in the region of 800 nm to 2600 nm. Cesium-containing composite tungsten oxide (Cs _0.33 WO ₃ ) can be obtained in the form of fine powder particles, and further dispersed in a solvent can be obtained. The organic dispersant is a binder resin used when the cesium-containing composite tungsten oxide fine particles are manufactured.

Although the cesium-containing composite tungsten oxide fine particles are suitable from the viewpoint of optical properties and weather resistance, etc., although they are temporarily dispersed when mixed with the curable compositions used in the present invention, according to the study by the present inventors, It was clarified that the agglomerates were allowed to stand for several hours or when the curable composition was cured. Then, the present inventors apply a solution of the cesium-containing composite tungsten oxide composition to the surface of the cured composition molded body and dry the solution, so that the absorption characteristics from 800 nm of the cesium-containing composite tungsten oxide are obtained. Found that can be granted to. The inventors have also found that the spectral transmission intensity can be adjusted by adjusting the coating thickness.

(1-3) Preparation method and curing method of curable composition The preparation method of the curable composition having near infrared absorption performance according to the present invention is not particularly limited and can be prepared by various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance. When the composition containing the components (a) to (c) described above is used as the curable composition (A), the first component (near-infrared absorbing material (B-1)) is the ( All components may be mixed and prepared after dissolving in component a) or component (c). An organic solvent solution of the near-infrared absorbing compound (B-1) is prepared and combined with component (a) or component (c) All components may be mixed and prepared after mixing and removing the organic solvent by devolatilization or the like.

In addition to the modified polyorganosiloxane compound, when using additives such as thermoplastic resins for the purpose of improving physical properties, these additives and a platinum compound that is a curing catalyst are mixed and stored in advance and immediately before curing. The respective predetermined amounts may be mixed with each other.

The thermosetting temperature can be variously set, but the lower limit of the preferable temperature is 30 ° C, more preferably 60 ° C, and still more preferably 90 ° C. The upper limit of preferable temperature is 250 degreeC, More preferably, it is 200 degreeC. When the reaction temperature is low, the reaction time for sufficient reaction is prolonged. If the reaction temperature is high, coloring or bulging may occur.

Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as necessary. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, rather than at a constant temperature, in that a cured product with less coloring and less distortion can be easily obtained.

The pressure during the reaction can be variously set as required, and the reaction can be performed under normal pressure, high pressure, or reduced pressure.

The shape of the cured product obtained by curing can be variously selected depending on the application, and is not particularly limited. For example, the shape of a lens, film, sheet, tube, rod, coating, bulk, etc. can do.

As the molding method, various methods including a conventional thermosetting resin molding method can be employed. For example, a casting method, a pressing method, a casting method, a transfer molding method, a coating method, a RIM method, a LIM method, or the like can be applied. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied.

In addition, in order to improve releasability from the mold, polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, polyethylene film, polytetrafluoroethylene film, polypropylene film, polyimide film, gold or surface-treated gold A mold etc. can be applied.

Various processing can be performed as necessary during molding. For example, in order to suppress voids generated during molding, a process of defoaming the composition or a partially reacted composition by centrifugation, decompression, or the like, a process of releasing the pressure once during pressing, or the like can be applied.

When the composition containing the components (a) to (c) described above is used as the curable composition (A), the ratio of the component (a) to the component (c) is [SiH of component (a)]. The ratio of the number of moles of carbon-carbon double bonds having reactivity with the group / the number of moles of SiH groups in the component (c)] is preferably a ratio such that the lower limit is 0.05 and the upper limit is 10. More preferably, the ratio is in the range of 0.1 and an upper limit of 5. When the amount is small, the crosslinking effect due to the reaction between the alkenyl group and the SiH group tends to be insufficient. When the amount is large, the unreacted component (A) may bleed from the cured product.

(1-4) Additives In the curable composition according to the present invention, various additives can be used depending on the purpose.

(Curing retarder)
In the curable composition according to the present invention, a curing retarder can be used for the purpose of improving the storage stability or adjusting the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide. These may be used alone or in combination of two or more.

Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like.

Examples of the organic phosphorus compound include triorganophosphine, diorganophosphine, organophosphine, and triorganophosphite.

Examples of organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like.

Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like.

Examples of tin compounds include stannous halide dihydrate and stannous carboxylate.

Examples of organic peroxides include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.

Among these curing retarders, from the viewpoint of good retarding activity and easy availability of raw materials, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.

Amount of the curing retarder, towards hydrosilylation catalyst 1 mole to be used, the lower limit 10 ^-1 mol, the range of the upper limit 10 ³ moles and preferably, more preferably the lower limit 1 mol, the range of the upper limit 50 mol. When there is little addition amount, the desired storage stability and the gelatinization inhibitory effect at the time of vacuum devolatilization are not acquired. If the amount added is large, it can be a curing inhibitor during the curing reaction.

Moreover, these gelation inhibitors may be used alone or in combination of two or more.

(Heat stabilizer)
The curable composition according to the present invention preferably uses a heat stabilizer for the purpose of improving the reflow resistance. Any thermal stabilizer may be used as long as it can prevent thermal degradation and oxidation degradation of the cured product obtained by curing the curable composition according to the present invention. The common antioxidant which is used can be used suitably. Examples of general antioxidants include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

Examples of hindered phenol compounds include n-octadecyl 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl 3- (3′-methyl-5 ′ -T-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] 2,2'-methylene-bis (4-methyl-t-butylphenol), triethylene glycol bis [3- (3-t-butyl-5-methyl-4- Loxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-methyl-5′-t-butyl-4 '-Hydroxyphenyl) propionyl] diamine, N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl] hydrazine, N-salicylo Ru-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like.

Preferably, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl- 4-hydroxyphenyl) propionate] methane and the like.

As the phosphite compound, those in which at least one PO bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-t-butylphenyl) phosphite, tetrakis (2 , 6-Di-t-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis ( 4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris ( 2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, 4,4′- Seo propylidene bis (phenyl - dialkyl phosphite), and the like.

Among them, tris (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl) -4-Methylphenyl) pentaerythritol di-phosphite, tetraphenyl-4,4'-biphenylene phosphite and the like can be preferably used.

Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate ), Pentaerythritol tetrakis (3-dodecyl thiopropionate), pentaerythritol tetrakis (3-octadecyl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate), pentaerythritol tetrakis (3-stearyl thiopro) Pionate). These may be used alone or in combination of two or more.

(Thermoplastic resin)
Various thermoplastic resins may be added to the curable composition according to the present invention for the purpose of modifying the characteristics.

Various thermoplastic resins can be used. For example, polymethyl methacrylate resins such as methyl methacrylate homopolymers or random, block, or graft polymers of methyl methacrylate and other monomers (for example, Hitachi) OPTRETZ etc. manufactured by Kasei Co., Ltd.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3 , 3,5-trimethylcyclohexylidene bisphenol etc. as a monomer structure polycarbonate resin such as polycarbonate resin (for example, Panlite manufactured by Teijin Ltd.), norbornene derivative, vinyl monomer etc. alone or copolymerized Resins, cycloborn-based resins such as ring-opening metathesis polymerization of norbornene derivatives, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene Olefin-maleimide resins such as imide-maleimide copolymer (eg, TI-PAS manufactured by Tosoh Corporation), bisphenol A, bisphenol such as bis (4- (2-hydroxyethoxy) phenyl) fluorene, diethylene glycol, etc. Polyester resins such as polyester (for example, DuPont linite) obtained by polycondensation of diols with phthalic acids such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids, polyethersulfone resins, polyarylate resins, polyvinyl acetal resins , Poly Styrene resins, polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the resulting cured product is likely to be high, it is preferable to have one or more crosslinkable groups per molecule on average.

The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight may be 10,000 or less in that the compatibility with the mixture of component (a) and component (c) tends to be good. Preferably, it is 5000 or less. On the contrary, the number average molecular weight is preferably 10,000 or more, more preferably 100,000 or more in that the resulting cured product is likely to be tough. The molecular weight distribution (weight average molecular weight / number average molecular weight) is not particularly limited, but the molecular weight distribution is preferably 3 or less in that the viscosity of the mixture tends to be low and moldability tends to be good. More preferably, it is more preferably 1.5 or less.

The blending amount of the thermoplastic resin is not particularly limited, but a preferable range of use amount is 5 to 50% by weight, more preferably 10 to 30% by weight of the entire curable composition. If the amount added is small, the resulting cured product tends to be brittle. If the amount added is large, the heat resistance (elastic modulus at high temperature) tends to be low.

As the thermoplastic resin, a single resin may be used, or a plurality of resins may be used in combination.

The thermoplastic resin may be dissolved in the component (a) and / or the component (c) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. Then, it may be in a dispersed state. Further, the thermoplastic resin may be directly dissolved in the component (a) and / or the component (c), or may be mixed uniformly using a solvent, etc. It may be in a mixed state.

When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the preferable lower limit of the average particle diameter is 10 nm, and the preferable upper limit of the average particle diameter is 10 μm. The particle size may have a distribution and may be monodispersed or have a plurality of peak particle sizes, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. The particle diameter variation coefficient is preferably 10% or less.

(Filler)
In the range which does not impair transparency, you may add a filler to the curable composition which concerns on this invention.

Various fillers are used. For example, silica-based fillers such as quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, silicon nitride, silver powder, etc. Inorganic fillers such as alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloon As fillers for conventional sealing materials such as epoxy-based fillers, fillers that are generally used and / or proposed can be mentioned.

(Radical inhibitor)
A radical inhibitor may be added to the curable composition according to the present invention. Examples of radical inhibitors include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondarybutyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine.

In addition, these radical inhibitors may be used alone or in combination of two or more.

(UV absorber)
An ultraviolet absorber may be added to the curable composition according to the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, etc. Is mentioned. Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(solvent)
When the curable composition according to the present invention has a high viscosity, it can be used by dissolving in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), glycol solvents such as ethylene glycol diethyl ether, chloroform, methylene chloride, A halogen-based solvent such as 1,2-dichloroethane can be preferably used.

Of these, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

The amount of solvent to be used can be appropriately set, but the lower limit of the preferred amount of use with respect to 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as viscosity reduction. If the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also in terms of cost. It is disadvantageous and the industrial utility value decreases.

These solvents may be used alone or as a mixed solvent of two or more.

(Other additives)
In addition, the curable composition according to the present invention includes an adhesion-imparting agent, a colorant, a mold release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, a repellency inhibitor, Antimony-bismuth and other ion trapping agents, thixotropic agents, tackifiers, storage stability improvers, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, reactive diluents, conductivity enhancers, Antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity-imparting agents, physical property modifiers and the like within a range that does not impair the purpose and effect of the present invention Can be added.

(1-5) Coating method As a method for forming a layer containing a near-infrared absorbing compound (B-2) on the surface of a molded article containing a nonionic infrared-absorbing compound (B-1), a near-infrared ray can be used. Examples thereof include a method of applying the absorbing compound (B-2) to the surface of the molded body.

The solvent used when applying the near-infrared absorbing compound (B-2) is an aliphatic hydrocarbon solvent selected from hexane and heptane; an aromatic hydrocarbon solvent selected from anisole, mesitylene, toluene, and xylene; Ketone solvents selected from methyl isobutyl ketone, cyclohexanone and acetone; ether solvents selected from tetrahydrofuran, dioxolane and dioxane; amide solvents selected from 1-methyl-2-pyrrolidinone, dimethylacetamide and dimethylformamide; and silicon solvents However, from the viewpoint of dispersibility and film-forming property of the near-infrared absorbing compound (B-2), aromatic carbonization selected from anisole, mesitylene, toluene, and xylene Hydrogen solvent is preferred , Especially anisole preferred among this.

Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used. The method applied in this method is most preferably a wire bar coating.

(1-6) Applications The near-infrared absorbing resin composition according to the present invention can be molded into a desired shape and used for various optical materials.

Here, the optical material is a material used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material, and is specifically as follows.

Main applications include lenses that absorb and cut near infrared rays (camera lenses such as digital cameras, mobile phones, and in-vehicle cameras, optical lenses such as f-θ lenses and pickup lenses), and optics for semiconductor light receiving elements. Filters, near-infrared absorbing films that block heat rays for energy saving and their coating agents and near-infrared absorbing plates, agricultural infrared-absorbing film coating agents for selective use of sunlight, near-infrared absorbing heat Recording media used, near-infrared cut filter for electronic equipment, near-infrared filter for photography, protective glasses, sunglasses, heat ray blocking film, optical recording compound (dye), optical character reading recording, confidential document copy prevention, electrophotographic photosensitive Used for body, laser welding, etc. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

The present invention can also be restated as follows.

(1) A near-infrared absorbing compound (B-2) is formed on the surface of a molded product obtained from a transparent resin composition comprising the curable composition (A) containing a nonionic near-infrared absorbing compound (B-1). A near-infrared absorbing material comprising a layer containing

(2) The curable composition (A) is selected from any one of a curable silicone composition, a curable epoxy silicone composition, a curable acrylic composition, a curable norbornene composition, and a curable polyimide composition. The near-infrared absorbing material according to (1), wherein

(3) The curable composition (A) is
(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule;
(B) an organosiloxane compound containing at least two SiH groups in one molecule;
(C) a hydrosilylation catalyst,
Is contained as an essential component, The near-infrared absorption material as described in (1) or (2) characterized by the above-mentioned.

(4) The curable composition (A) contains 0.001 to 0.1 parts by weight of the nonionic near-infrared absorbing compound (B-1) with respect to 100 parts by weight (1) to The near infrared ray absorbing material according to any one of (3).

(5) The near-infrared absorbing material according to any one of (1) to (4), wherein the nonionic near-infrared absorbing compound (B-1) is a perylene compound and / or a quatarylene compound. .

(6) The near-infrared absorbing material according to any one of (1) to (5), wherein the near-infrared absorbing compound (B-2) is a composite tungsten oxide compound.

(7) A solution in which the near-infrared absorbing compound (B-2) is dispersed so as to be 1 to 50 parts by weight with respect to 100 parts by weight of the organic solvent is prepared and applied. 1. The method for producing a near infrared ray absorbing material according to any one of 1) to (6).

(8) The coating method includes spin coating, casting, micro gravure coating, gravure coating, knife coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. The method for producing a near-infrared absorbing material according to any one of (1) to (7), wherein at least one of the above is used.

(9) An aliphatic hydrocarbon solvent in which the organic solvent is selected from hexane and heptane; an aromatic hydrocarbon solvent selected from anisole, mesitylene, toluene, and xylene; a ketone selected from methyl isobutyl ketone, cyclohexanone, and acetone An ether solvent selected from tetrahydrofuran, dioxolane and dioxane; an amide solvent selected from 1-methyl-2-pyrrolidinone, dimethylacetamide and dimethylformamide; and at least one selected from the group consisting of silicon solvents The method for producing a near-infrared absorbing material according to any one of (1) to (8).

(10) The near-infrared absorbing material according to any one of (1) to (9), wherein a film thickness of the applied composite tungsten oxide composition is in a range of 0.1 μm to 10 μm. .

(11) The near-infrared absorbing material according to any one of (1) to (10), wherein the composite tungsten oxide is a cesium-containing composite tungsten oxide.

(12) An optical material, wherein the near-infrared absorbing material described in (1) to (11) is used as an infrared shielding body.

According to the present invention, a near-infrared absorbing compound is dispersed in a transparent resin, and in addition, by applying another near-infrared absorbing compound coating to the resin molding, it has high visible light transmittance and near-infrared absorbing characteristics, and solder It is possible to provide a near-infrared absorbing resin material that does not substantially change optical characteristics even under high temperature conditions such as a reflow process. Moreover, the curable composition applied to the near-infrared absorbing material of the present invention maintains the original moldability and processability of the resin and can be formed into a desired shape.

[2. Near-infrared absorbing material (II)]
The near-infrared absorbing material (II) includes, as the near-infrared absorbing compound (B), at least one selected from the group consisting of a composite tungsten oxide compound, a phthalocyanine-based compound, and a naphthalocyanine-based compound, a perylene-based compound, and quaterrylene It is obtained by applying a curable coating agent having infrared absorbing ability, which contains at least one selected from the group consisting of a system compound, to at least one surface of a transparent substrate, evaporating the solvent, and then curing.

(2-1) Curable coating agent The curable coating agent used in the production of the near-infrared absorbing material (II) includes a composite tungsten oxide compound, a phthalocyanine-based compound, and a naphthalocyanine-based compound as the near-infrared absorbing compound (B). It includes at least one selected from the group consisting of compounds and at least one selected from the group consisting of perylene compounds and quatarylene compounds.

The curable coating agent preferably further includes a curable composition (A), and the near-infrared absorbing compound (B) is preferably dissolved or dispersed in the curable composition (A).

The curable coating agent preferably contains a solvent (C).

(2-1-1) Curable composition (A)
In the present invention, the curable composition (A) described above in “(1-1) Curable composition (A)” can be used as the curable composition (A).

When the composition containing the components (a) to (c) described above is used as the curable composition (A), the ratio of the component (a) to the component (c) is [the reaction with the SiH group of the component (a). The ratio of the number of moles of carbon-carbon double bond having a property / the number of moles of SiH groups in the component (c)] is preferably a ratio such that the lower limit is 0.05 and the upper limit is 10. The ratio is more preferably in the range of the upper limit of 5. When the amount is small, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group tends to be insufficient. When the amount is large, the unreacted component (a) may bleed from the cured product.

(2-1-2) Near-infrared absorbing compound (B)
The near-infrared absorbing material (II) is selected from the group consisting of “at least one selected from the group consisting of complex tungsten oxide compounds, phthalocyanine compounds, and naphthalocyanine compounds” and “perylene compounds and quatarylene compounds” Are used together, and both of them are classified as near-infrared absorbing compounds. The present inventors have found that the above combination is excellent among many near infrared absorbing compounds, and have reached the present invention.

Near-infrared rays generally represent a wavelength band of 700 to 2500 nm, but a region that needs to be cut in a light-sensitive region of an optical element represents a near-infrared wavelength band of approximately 700 to 1100 nm. The near-infrared absorbing dye of the present application is a compound having a near-infrared absorbing ability, but can cover absorption in the near-infrared region of about 700 to 1100 nm.

The near-infrared absorbing compound (B) preferably has a high heat resistance with a thermal decomposition temperature of 260 ° C. or higher, preferably 300 ° C. or higher, from the viewpoint of imparting thermal stability and reflow resistance.

As the quatarylene compound, perylene compound, composite tungsten oxide compound, phthalocyanine compound and naphthalocyanine compound used in the near infrared absorbing material (II), the compounds described above in “(1-2) Near infrared absorbing compound” can be used. Each can be used.

In addition, it is preferable to use the compound which has the solubility to a solvent (C) and a curable composition (A) as a near-infrared absorption compound (B). When it is soluble in the solvent (C) and the curable composition (A), the preparation of the curable coating liquid is facilitated and the light transmittance in the visible light region is increased. The solubility of the near-infrared absorbing compound (B) in the solvent (C) and the curable composition (A) is such that the total amount of the solvent (C) and the curable composition (A) is 100% by mass. It is suitable that it is 0.001 mass% or more.

In addition to the above, for example, aminothiol nickel complex compound; anthraquinone compound; cyanine compound; squarylium compound; thiol nickel complex compound; triarylmethane compound; naphthoquinone compound; nitroso compound and metal complex thereof; Inorganic nano-dye hybrid system; organic materials such as amino compounds; tin oxide doped with carbon black, antimony oxide or indium oxide, which are inorganic materials; oxides of metals belonging to Group 4, 5 or 6 of the periodic table; Carbides or borides; imonium compounds; diimonium compounds; aminium salt compounds and the like can be used in combination. Moreover, these can be utilized according to the required heat resistance conditions, and may be used independently and may be used together 2 or more types.

Examples of the amount of the near infrared absorbing compound used include the range described above in “(1-2) Near infrared absorbing compound”.

Further, as the near infrared absorbing compound (B), from the viewpoint of heat resistance, it is preferable to further use various inorganic fine particles described above in “(1-2) Near infrared absorbing compound”.

Although the cesium-containing composite tungsten oxide fine particles are preferable from the viewpoint of optical properties and weather resistance, etc., the present inventors have studied, but when dispersed directly into the curable compositions to be used, It was clarified that when it was allowed to stand for about an hour, it separated and formed a precipitate. Here, the inventors can improve the dispersion state by adding a solvent to the mixture of the cesium-containing composite tungsten oxide fine particles and the cured composition, and further have another absorption having an absorption at 650 to 850 nm. By adding an infrared absorbing compound, the inventors have invented a curable coating liquid having a near infrared absorption characteristic of 700 to 1100 nm. It was also discovered that the spectral transmission intensity can be adjusted by adjusting the coating thickness.

(2-1-3) Solvent (C)
Solvents that can be used in the curable coating agent according to the present invention are not particularly limited, and specific examples include aliphatic hydrocarbon solvents selected from hexane and heptane; anisole, mesitylene, toluene, and Aromatic hydrocarbon solvents selected from xylene; alcohol solvents such as iso-propyl alcohol, n-butyl alcohol and propylene glycol methyl ether; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; methyl ethyl ketone and methyl isobutyl ketone A ketone solvent selected from cyclohexanone and acetone; an ether solvent selected from dioxane such as tetrahydrofuran, diethyl ether, dioxolane and 1,4-dioxane; 1-methyl-2-pyrrolidinone, dimethylacetate Amide solvent selected from amide and dimethylformamide; silicon solvent; glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane At least one kind of solvent selected from halogen-based solvents such as can be suitably used. Among these, anisole and methyl ethyl ketone are preferable.

(2-2) Preparation method and curing method of curable coating agent (Preparation method of curable coating agent)
The preparation method of the curable coating agent which has near-infrared absorption performance based on this invention is not specifically limited, It can prepare with various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance. Moreover, after dissolving in the curable composition (A) according to the present invention, all components may be mixed and prepared, and an organic solvent solution of the near-infrared absorbing compound (B) is prepared, and the curable composition (A) is prepared. It may be prepared by mixing with ingredients and adding a solvent.

The near-infrared absorbing compound (B) is preferably added in an amount of 0.01 to 100 parts by weight, more preferably 0.05 to 30 parts by weight, relative to 100 parts by weight of the curable composition (A). Further, 0 to 1000 parts by weight of the solvent (C) is preferably added to 100 parts by weight of the curable composition (A), more preferably 1 to 900 parts by weight, and more preferably 5 to 800 parts by weight. It is more preferable to add 100 to 400 parts by weight.

The mixture of the near-infrared absorbing compound (B) and the curable composition (A) may be coated as it is without adding the solvent (C). When additives such as thermoplastic resins are used for the purpose of improving physical properties, these additives and a platinum compound as a curing catalyst are mixed and stored in advance, and each predetermined amount is mixed immediately before curing. May be prepared. The viscosity of the curable coating agent is appropriately adjusted depending on the addition ratio of the curable composition, near-infrared absorbing dye, organic solvent, additive, etc., but the range is 2 to 200 Pa · s (Pascal · second). For example, when application to a glass substrate is performed by a spin coating method, 2 to 5 Pa · s is preferable. In order to obtain a film thickness of 10 to 20 μm by coating once by screen printing, 50 to 200 Pa · s is preferable. When using a blade coater method, a die coater method, or the like, 2 to 20 Pa · s is preferable.

The solvent (C) used for preparing the curable coating solution is preferably the solvent described above in “(1-5) Coating method”.

(Coating film curing method)
The thermosetting temperature can be variously set, but the lower limit of the preferable temperature is 30 ° C, more preferably 60 ° C, and still more preferably 90 ° C. The upper limit of preferable temperature is 250 degreeC, More preferably, it is 200 degreeC. When the reaction temperature is low, the reaction time for sufficient reaction is prolonged. If the reaction temperature is high, coloring or bulging may occur.

(Coating method)
Examples of the coating method include dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method, air knife coating method, curtain coating method, etc. A known coating method can also be used. The method applied in this method is most preferably a wire bar coating.

(Solvent evaporation method)
The method for removing the solvent (C) is not particularly limited, but it is preferably performed by evaporating the solvent. Examples of the method for evaporating the solvent include methods such as heating, decompression, and ventilation. Among them, it is preferable to evaporate the solvent by heating from the viewpoint of production efficiency and handleability, and it is more preferable to evaporate the solvent by heating with ventilation. Specifically, it is preferable to perform preliminary drying at 80 to 100 ° C. for 30 minutes to 2 hours, and heat treatment at 180 to 260 ° C. for 10 minutes to 30 minutes.

The transparent base material that coats the near-infrared coating agent only needs to have both transparency and heat resistance, and a polycarbonate film, a polyimide film, a silicone film, or the like can be applied.

(2-3) Additives In the curable coating agent of the present invention, various additives listed in “(1-4) Additives” can be used in various ranges according to various purposes. Can be used within.

(2-4) Applications The curable coating agent of the present invention can be used after being applied to various optical materials and dried. The optical material here is synonymous with the optical material described in the section “(1-5) Applications”.

The present invention can also be restated as follows.

(1) A curable coating agent having a near-infrared absorbing ability, comprising a composite tungsten oxide and a compound selected from the group consisting of a perylene-based compound and a quatarylene-based compound as the near-infrared absorbing compound (B).

(2) The curable coating agent having near infrared absorption ability according to (1), wherein the composite tungsten compound is a cesium-containing tungsten oxide.

(3) The solvent (C) is contained in an amount of 0 to 1000 parts by weight with respect to 100 parts by weight of the curable composition (A) and 0.01 to 100 parts by weight of the near infrared ray absorbing compound (B). ) Or a curable coating agent having near infrared absorption ability according to (2).

(4) The curable composition (A) is selected from the group consisting of a curable silicone composition, a curable epoxy silicone composition, a curable acrylic composition, a curable norbornene composition, and a curable polyimide composition. The curable coating agent having near-infrared absorbing ability according to (3), which is characterized in that it exists.

(5) The curable composition (A) is
(A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule;
(B) a hydrosilylation catalyst,
(C) an organosiloxane compound containing at least two SiH groups in one molecule;
The curable coating agent having near infrared absorption ability according to (3) or (4), characterized in that is an essential component.

(6) Solvent (C) is hexane, heptane, anisole, mesitylene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, tetrahydrofuran, dioxolane, dioxane, 1-methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide And a curable coating agent having near infrared absorption ability according to any one of (3) to (5), which is at least one selected from the group consisting of silicon solvents.

(7) Obtained by applying the curable coating agent having near infrared absorption ability according to any one of (1) to (6) to at least one surface of a transparent substrate, evaporating the solvent, and then curing the coating. Near infrared absorbing material.

(8) An optical material characterized in that the near-infrared absorbing material obtained in (7) is used as a near-infrared shield.

The curable coating agent having near infrared absorption ability of the present invention can be applied regardless of the shape of the transparent substrate, or the optical property does not substantially change even under high temperature conditions such as a sand reflow process. In order to provide an infrared absorbing material, it is useful as an optical material that requires high heat resistance and an infrared shielding function.

[3. Near-infrared absorbing material (III)]
Near-infrared absorbing material (cured product) (III) comprises (a) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule, (b) a hydrosilylation catalyst, (C) Near-infrared absorption comprising a compound containing at least two SiH groups in one molecule, (d) a quatarylene compound, and at least one compound selected from a phthalocyanine compound and a naphthalocyanine compound And a curable composition containing the curable composition.

(3-1) Curable composition The curable composition used in the production of the near-infrared absorbing material (III) comprises (a) at least a carbon-carbon double bond having reactivity with a SiH group in one molecule. Two organic compounds, (b) a hydrosilylation catalyst, (c) a compound containing at least two SiH groups in one molecule, (d) a quatarylene compound, a phthalocyanine compound, and a naphthalocyanine compound And a near-infrared absorbing composition containing at least one compound selected from the group consisting of: Thereby, it becomes possible to provide a material having near infrared absorptivity and having both moldability and reflow resistance.

As the components (a) to (c), the components (a) to (c) described above in “(1-1-5) curable silicone composition” can be used.

Component (d) will be described below.

Near-infrared rays generally represent a wavelength band of 700 to 2500 nm, but a region that needs to be cut in a light-sensitive region of an optical element represents a near-infrared wavelength band of approximately 700 to 1100 nm. The component (d) of the present application is a compound having near-infrared absorption ability, but can cover absorption in the near-infrared region of about 700 to 1100 nm.

Therefore, in the near-infrared absorbing material (III), as the component (d), in addition to the quartalylene compound and / or the perylene compound, at least two kinds selected from a phthalocyanine compound or a naphthalocyanine compound, that is, at least 3 It is preferable to mix and combine the specific compounds of the species.

Component (d) preferably has a high heat resistance with a thermal decomposition temperature of 200 ° C. or higher, preferably 260 ° C. or higher, from the viewpoint of providing thermal stability and reflow resistance.

As the quatarylene compound, perylene compound, phthalocyanine compound and naphthalocyanine compound used in the near infrared absorbing material (III), the compounds described above in “(1-2) Near infrared absorbing compound” can be used. it can.

Component (d) is preferably a compound having solubility in an organic solvent, component (a) or component (c). When it is soluble in the organic solvent, component (a) or component (c), the preparation of the curable composition is facilitated and the light transmittance in the visible light region is increased. The solubility of the component (d) with respect to the organic solvent, the component (a), or the component (c) is 0.001% by mass or more when the organic solvent, the component (a) or the component (c) is 100% by mass. Is preferred.

The organic solvent that can be used in the curable composition is not particularly limited. For example, aromatic solvents such as toluene and xylene; alcohol solvents such as iso-propyl alcohol, n-butyl alcohol, and propylene glycol methyl ether; acetic acid Ester solvents such as butyl, ethyl acetate and cellosolve acetate; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; one or more of dimethylformamide and the like It is done.

The amount of component (d) used is preferably 0.0005 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight as the total of component (a) and component (c). Is preferred. More preferably, it is 0.0015 weight part or more, and 10 weight part or less, More preferably, it is 0.002 weight part or more, and 7 weight part or less.

If the amount of the component (d) added is small, the cured product formed from the cured composition having near-infrared absorption performance may not exhibit sufficient near-infrared absorption performance. There is a possibility that light may be scattered due to a possibility of decrease of the density or aggregation.

The ratio of component (a) to component (c) is [number of moles of carbon-carbon double bond reactive with SiH group of component (a) / number of moles of SiH group of component (c)]. Of the lower limit of 0.05 and the upper limit of 10 is preferable, and the lower limit of 0.1 and the upper limit of 5 is more preferable. When the amount is small, the crosslinking effect due to the reaction between the alkenyl group and the SiH group tends to be insufficient. When the amount is large, the unreacted component (A) may bleed from the cured product.

(3-2) Preparation method and curing method of curable composition The preparation method of the curable composition having near infrared absorption performance according to the present invention is not particularly limited, and can be prepared by various methods, for example, The method described above in “(1-3) Preparation method and curing method of curable composition” can be appropriately used.

Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance. Alternatively, all the components may be mixed and prepared after the component (d) is dissolved in the component (a) or the component (c) of the present invention, an organic solvent solution of the component (d) is prepared, and the component (a) Or after mixing with (c) component and removing an organic solvent by a devolatilization process etc., all components may be mixed and prepared.

(3-3) Additives The curable composition used in the production of the near-infrared absorbing material (III) may contain various additives listed in “(1-4) Additives” according to various purposes. 1-4) Additives ”can be used within the range mentioned above.

(3-4) Applications A cured product obtained by curing the near-infrared absorption curable composition of the present invention can be molded into a desired shape and used for various optical materials. The optical material here is synonymous with the optical material described in the section “(1-5) Applications”.

The present invention can also be restated as follows.

(1) (a) an organic compound having two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(B) a hydrosilylation catalyst,
(C) a compound having at least two SiH groups in one molecule, and
(D) at least two types of compounds selected from quartarylene compounds and phthalocyanine compounds or naphthalocyanine compounds;
A curable composition having near infrared absorption ability.

(2) The component (a) is represented by the following general formula (IV)

(In the formula, R ³ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least two R ³ may be SiH groups and Including a carbon-carbon double bond having the reactivity of
The curable composition which has the near-infrared absorptivity as described in (1) which is an organic compound represented by these.

(3) The component (a) is represented by the following general formula (III)

(Wherein R ⁴ represents an organic group which may be substituted with a monovalent oxygen, nitrogen, sulfur or halogen atom having 1 to 50 carbon atoms, and each R ⁴ may be different or the same. May be.)
The curable composition which has the near-infrared absorptivity as described in (1) which is an organic compound which has a structure represented by these.

(4) The component (c) is
(Α) an organic compound containing one or more carbon-carbon double bonds having reactivity with SiH groups in one molecule;
(Β) a polyorganosiloxane having a chain, cyclic, branched or cage structure having at least three SiH groups in one molecule;
The curable composition having near infrared absorption ability according to any one of (1) to (3), which is a compound obtainable by hydrosilylation reaction.

(5) The component (α) is represented by the following general formula (IV)

(Wherein R ³ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ may be a SiH group and Including a carbon-carbon double bond having the reactivity of
The curable composition which has the near-infrared absorptivity as described in (4) which is an organic compound represented by these.

(6) The component (α) is represented by the following general formula (X)

(Wherein R ⁴ represents an organic group which may be substituted with a monovalent oxygen, nitrogen, sulfur or halogen atom having 1 to 50 carbon atoms, and each R ⁴ may be different or the same. May be.)
The curable composition having near infrared absorption ability according to (4), which is an organic compound having a structure represented by:

(7) (β) At least one of chain, cyclic, branched and cage polyorganosiloxane having at least three SiH groups in one molecule is represented by the following general formula (VI)

(Wherein R ¹⁴ and R ¹⁵ represent an organic group having 1 to 10 carbon atoms, n represents 3 to 10, and m represents a number of 0 to 10)
The curable composition having near infrared absorption ability according to any one of (4) to (6), which is a compound containing a polyorganosiloxane compound having a SiH group represented by:

(8) A cured product obtained by curing the curable composition having near infrared absorption ability according to any one of (1) to (7).

According to the present invention, it is possible to provide a near-infrared absorbing material having reflow resistance. Moreover, the curable composition applied to the near-infrared absorbing material of the present invention maintains the original moldability and processability of the resin, and can be formed into a desired shape.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following. In addition, the reaction rate of the allyl group in the synthesis example was measured using a 300 MHz-NMR apparatus manufactured by Varian Technologies Japan Limited, adding the reaction solution diluted to about 1% with deuterated chloroform to the NMR tube, Calculated from the peak ratio of the methylene group derived from the unreacted allyl group and the methylene group derived from the reacted allyl group, and the content of the SiH group as the component (c) is 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited. Was obtained as the SiH group value (mmol / g) in terms of 1,2-dibromoethane.

[Synthesis Example 1]
A stirrer, a dropping funnel, and a condenser tube were set in a 5-L four-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion was purged with nitrogen, and then heated and stirred in a 120 ° C. oil bath. A mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless transparent liquid “Reactant E”.

The content of SiH groups determined by ¹ H-NMR was 8.8 mmol / g. Although the product is a mixture, it contains as a main component the following compound having 9 SiH groups per molecule, which is the component (c) in the present invention.

[Synthesis Example 2]
A 500 mL four-necked flask was charged with 100 g of toluene and 57.49 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed solution of 12.7 g of diallyl monoglycidyl isocyanurate, 12.7 g of toluene and 0.0112 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 30 minutes. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless transparent liquid “Reaction product F”.

The content of SiH groups determined by ¹ H-NMR was 7.6 mmol / g. Although the product is a mixture, it contains, as a main component, the following compound having 6 SiH groups per molecule, which is the component (c) of the present invention.

[Synthesis Example 3]
600 g of toluene and 600 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L four-neck flask, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 90 ° C. A mixed solution of 73.5 g of divinylbenzene, 73.5 g of toluene and 0.006 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 1 hour. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more, and the reaction was terminated by cooling.

Toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off under reduced pressure at 60 ° C. for 2 hours and at 80 ° C. for 2 hours to obtain a colorless transparent liquid “Reaction product G”.

The content of SiH groups determined by ¹ H-NMR was 9.8 mmol / g. Although the product is a mixture, it contains, as a main component, the following compound having 6 SiH groups per molecule, which is the component (c) of the present invention.

1. Near-infrared absorbing material (I)
[Examples 1 to 4, Comparative Examples 1 to 4]
(Step 1. Preparation of cured product)
A curable composition was prepared with the formulation shown in Table 1 for the reactant E obtained in Synthesis Example 1. Specifically, (a) component 24.4 g, near-infrared absorbing compound (B-1) [“Lumogen IR 765” and / or “Lumogen IR 788” (made by BASF) as a nonionic near-infrared absorbing compound, “Kayasorb CY-40MC (F) (manufactured by Nippon Kayaku Co., Ltd.)” as an ionic near-infrared absorbing dye was mixed in the added number of parts shown in Table 1, and the mixture was stirred and degassed under reduced pressure. 0.12 g of the reaction product E obtained in 2 was added, and a mixture of 35.6 g of component (b) and 0.12 g of a retarder was further added to obtain a curable composition.

In addition, triallyl isocyanurate was used as the component (a), and the reactant E was used as the component (b).

Next, the obtained curable composition is poured into a cell prepared by sandwiching a 1 mm-thick silicone rubber sheet as a spacer between two glass plates, and heated in a hot air oven at 120 ° C. for 40 minutes as pre-curing. As a post-curing, heating was performed in a hot air oven at 180 ° C. for 15 minutes to obtain a plate-shaped cured product. All of the obtained cured products were transparent and could be used as various optical materials. The physical properties are shown in Table 1.

(Step 2. Application of near-infrared absorber (B-2))
As the cesium-containing composite tungsten oxide, a powder containing 77% of an organic dispersant was used. An anisole solution of a cesium-containing composite tungsten oxide prepared to a concentration of 30% by weight or 35% by weight is placed on a wire bar (winding) on the plate-like cured product (8 × 8 × 0.6 mmt). No. 16) was used to prepare a coating film on each transparent cured product plate. This was dried at room temperature for 12 hours and then dried in an oven at 260 ° C. for 10 minutes. This was diced to a size of 10 × 30 mm, and the film thickness and transmission spectrum of the cesium-containing composite tungsten oxide coating were measured. The results are also shown in Table 1.

Example 5
(Step 1. Preparation of cured product)
As a hydrosilyl group-containing polysiloxane having a three-dimensional structure, 3.52 g of MQH-5 (hydrosilyl group content 1.7 mol / kg) manufactured by Clariant, and as a vinyl group-containing polysiloxane having a three-dimensional structure, MQV- 7 (vinyl group content 3.5 mol / kg) 7.84 g was added and mixed in a polypropylene cup. To this, 23.7 mg of a xylene solution of platinum vinylsiloxane complex (containing 3% by weight of platinum), 74.2 mg of tetramethylethylenediamine (0.1% xylene solution), 1-ethynyl-1-cyclohexanol (1% (Xylene solution) 76.9 mg was added and stirred. The perylene compound (Lumogen IR 788, manufactured by BASF) as the near-infrared absorbing compound (B-1) is 0.02 part by weight with respect to 100 parts by weight of the curable silicone composition. -Dioxolane solution was added. This solution was subjected to degassing with stirring under reduced pressure to obtain a curable silicone composition that was liquid at room temperature. Subsequently, this curable composition was poured into a cell prepared by sandwiching a 1 mm thick silicone rubber sheet as a spacer between two glass plates, pre-curing at 120 ° C. for 40 minutes, and post-curing at 180 ° C. for 15 minutes. The plate-like cured product having a thickness of 1 mm was obtained by heating in a hot air oven.

(Step 2. Application of near-infrared absorber (B-2))
As the cesium-containing composite tungsten oxide, a powder containing 77% of an organic dispersant was used. A cesium-containing composite tungsten oxide anisole solution prepared so as to have a concentration of 30% by weight or 35% by weight is placed on the plate-like cured product (8 × 8 × 0.6 mmt) with a wire bar (type 16). Was used to prepare a coating film on each transparent cured product plate. This was dried at room temperature for 12 hours and then dried in an oven at 260 ° C. for 10 minutes. This was diced to a size of 10 × 30 mm, and the film thickness and transmission spectrum of the cesium-containing composite tungsten oxide coating were measured. The results are also shown in Table 1.

(Measurement of film thickness)
The coating film thickness was measured using a metricon prism coupler measuring device. For samples with a thick coating thickness that cannot be measured with a prism coupler, the thickness of the substrate and the thickness of the coated sample were measured at N = 10 using a Mitutoyo linear gauge and averaged except for the minimum and maximum values. The thickness was calculated by subtracting the thickness of the substrate from the coated substrate.

(Reflow resistance test)
Various cured products are put into an oven (STH-120) manufactured by ESPEC, and after holding for 180 seconds at a sample actual temperature of 260 ° C., taking out from the oven and cooling to room temperature are repeated three times. The light transmittance (the following method) and the color change (visual observation) were measured.

(Light transmittance)
The cured product sample was measured at a scan speed of 300 nm / min using U-3300 manufactured by Hitachi, Ltd. Table 1 shows the average transmittance of 400 to 600 nm, the average transmittance of 500 nm, 750 to 950 nm, and the light transmittance (% T) at 770 nm.

From Table 1, the following characteristics can be understood. In other words, the curable composition contains a quartalylene or perylene compound that absorbs at 650 to 850 nm and has high heat resistance, and does not need to contain a cesium tungsten oxide compound that absorbs at 800 nm or more and has high heat resistance in the resin. It was exemplified that a near-infrared absorber having no substantial change in optical properties in the visible / near-infrared region even after the reflow heat test can be obtained by applying to the surface of the cured molded body (Examples 1 to 5).

When a cyanine compound having low heat resistance was used, the optical characteristics changed after the reflow test, and there was a problem in the stability of the optical characteristics (Comparative Example 1).

The cured product only kneaded with quartalylene or perylene compound has heat resistance, but has a low near-infrared cutting power of 750 to 950 nm (Comparative Examples 2 and 3). From Comparative Example 4, only cesium tungsten is applied. In this case, it was found that the 770 nm cutting force was low and there was a problem in performance.

The near-infrared absorbing materials obtained in Examples 1 to 5 have absorption over the entire wavelength range of 700 to 1100 nm, and the reflow is repeated three times by holding for 60 seconds at 260 ° C. and then cooling to room temperature. Before and after the test, the average light transmittance at 400 to 600 nm in the cured resin composition was 20% or less and the rate of change in transmittance at a wavelength of 750 nm was within ± 5%.

2. Near-infrared absorbing material (II)
(Production of transparent substrate)
To 24.4 g of component (a) triallyl isocyanurate, 0.12 g of a xylene solution of platinum divinyldisiloxane complex (containing 3 wt%) as component (b) was added. This was mixed with 35.6 g of component (c) obtained in Synthesis Example 1 and 0.12 g of a retarder (1-ethynylcyclohexanol) to obtain a curable composition that was liquid at room temperature. Subsequently, the curable composition was poured into a cell prepared by sandwiching a 1 mm-thick silicone rubber sheet as a spacer between two glass plates, and heated in a hot air oven at 120 ° C. for 40 minutes as pre-curing, As post-curing, heating was performed in a hot air oven at 180 ° C. for 20 minutes to obtain a 1 mm thick cured product. This was used as a transparent substrate.

Example 6
(C) Component 3 obtained in Synthesis Example 1 was added to 20 g of anisole solution containing 6 g of a cesium tungsten oxide composition containing a dispersant (1.4 g of cesium tungsten oxide component) and 2.2 g of triallyl isocyanurate as component (a). .3 g, 0.0225 g of a platinum divinyldisiloxane complex xylene solution (containing 3 wt%) as component (b) and 0.0225 g of a retarder 1-ethynyl-1-cyclohexanol were added and mixed. Using this as a mother liquor, a curable coating solution to which 0.01 g of a perylene compound (“Lumogen 788”, manufactured by BASF) was added was prepared.

A coating film was prepared from this curable coating solution on a transparent substrate (10 × 5 cm) using a wire bar (type 16). This was left in a fume hood at room temperature, the solvent was naturally dried and it was confirmed that there was no tackiness, and then the coating film was cured in an oven at 120 ° C. for 40 minutes and 180 ° C. for 15 minutes. The coated specimen was placed in an oven (STH-120) manufactured by ESPEC, and held for 180 seconds at a sample actual temperature of 260 ° C., then removed from the oven and cooled to room temperature three times.

The coated transparent substrate was measured at a scan speed of 300 nm / min using a Hitachi 3300-made Sakai-3300, and the light transmittance at 400 nm to 600 nm and 750 nm to 950 nm before and after the reflow resistance test (% T) was calculated. The results are shown in Table 2.

[Comparative Example 5]
The component (c) obtained in Synthesis Example 1 was added to 20 g of an anisole solution containing 1.0 g of a diimonium compound (“CIR-RL”, manufactured by Nippon Carlit) and 2.2 g of triallyl isocyanurate as the component (a). 3 g, 0.0225 g of a platinum divinyldisiloxane complex xylene solution (containing 3 wt%) as component (b) and 0.0225 g of a retarder 1-ethynyl-1-cyclohexanol were added and mixed. A curable coating solution was prepared by adding 0.01 g of a quatarylene compound (“Lumogen 765”, manufactured by BASF) to this. This was processed in the same manner as in Example 7 to produce an evaluation sample, and then a heat resistance test was performed. Subsequently, the light transmittance was calculated by measuring the sample spectra before and after the heat resistance test. The results are shown in Table 2.

[Comparative Example 6]
To 20 g of anisole solution containing 2.2 g of triallyl isocyanurate as component (a), 3.3 g of component (c) obtained in Synthesis Example 1, and xylene solution of platinum divinyldisiloxane complex as component (b) (3 wt. 0.0225 g) and a retarder 1-ethynyl-1-cyclohexanol 0.0225 g were added and mixed. A curable coating solution was prepared by adding 0.01 g of a quatarylene compound (“Lumogen 765”, manufactured by BASF) to this. This was coated by the same method as in Example 7 to produce an evaluation sample, and then a heat resistance test was performed. Subsequently, the light transmittance was calculated by measuring the sample spectra before and after the heat resistance test. The results are shown in Table 2.

From Table 2, the following characteristics can be understood. It is obtained from a curable coating agent containing a perylene compound (Lumogen 788) that absorbs at 650 to 850 nm and has high heat resistance as a near-infrared absorbing compound and cesium tungsten oxide that absorbs at 800 nm and has high heat resistance. It was exemplified that a near-infrared absorber having no substantial change in optical properties in the visible / near-infrared region was obtained even after the reflow heat test (Example 6).

The visible light transmittance and infrared ray cutting power were excellent in the combination of a perylene compound (Lumogenｇ788) and a cesium tungsten compound. When a diimonium dye having low heat resistance was used, the optical characteristics changed after the reflow test, and there was a problem in stability (Comparative Example 5). A curable coating agent containing only a quaterrylene compound has heat resistance, but has a low near-infrared cutting power of 700 to 950 nm (Comparative Example 6), and has a problem in performance.

The near-infrared absorbing material obtained in Example 6 has absorption in the entire wavelength range of 700 to 1100 nm, and before and after the reflow test in which the operation of holding at 260 ° C. for 60 seconds and then cooling to room temperature is repeated three times. In the cured resin composition, the average light transmittance at 400 to 600 nm was 20% or less, and the rate of change in transmittance at a wavelength of 750 nm was within ± 5%.

3. Near-infrared absorbing material (III)
[Examples 7 to 8, Comparative Examples 7 to 14]
A curable composition was prepared with the composition shown in Table 3 for the reactants E, F, and G obtained in Synthesis Example 1, Synthesis Example 2, and Synthesis Example 3. In the preparation method, the component (a) and the component (d) were dissolved in 1,3-dioxolane and mixed. Thereafter, 1,3-dioxolane as a solvent was distilled off by evaporation, and the component (c) was added thereto. Separately, a mixture of component (b) and a retarder was further added to obtain a curable composition.

The curable composition was poured into a cell prepared by sandwiching the obtained curable composition between two glass plates with a 1 mm thick silicone rubber sheet as a spacer, and pre-cured at 120 ° C. for 40 minutes in a hot air oven. A cured product was obtained by heating and heating in a hot air oven at 180 ° C. for 15 minutes as post-curing. All of the obtained cured products were transparent and could be used as various optical materials. The physical properties are shown in Table 3.

(Reflow resistance test)
The cured product cut to 10 × 30 mm with a diamond cutter was placed in an oven (STH-120) manufactured by ESPEC, held at a sample actual temperature of 260 ° C. for 60 seconds, then removed from the oven and cooled to room temperature. This operation was repeated three times, and the light transmittance before and after the test (the following method), color change (visual observation), and thermal deformation (measured with calipers to confirm the change) were measured.

(Light transmittance)
A cured product cut to 10 × 30 mm with a diamond cutter was measured using a U-3300 manufactured by Hitachi, Ltd. at a scan speed of 300 nm / min, and light transmittance (% T) at 550, 750 and 850 nm. Was measured. The results are shown in Table 3.

In addition, “◯” in the physical properties of the cured product in the table indicates that there is no change in appearance dimension or color tone. Moreover, the color tone (before reflow) of the cured product properties is all transparent.

The near-infrared absorbing materials obtained in Examples 7 to 8 have absorption over the entire wavelength range of 700 to 1100 nm, and are reflowed by repeating the operation of holding at 260 ° C. for 60 seconds and then cooling to room temperature three times. Before and after the test, the average light transmittance at 400 to 600 nm in the cured resin composition was 20% or less and the rate of change in transmittance at a wavelength of 750 nm was within ± 5%.

The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

The near-infrared absorbing material of the present invention does not substantially change in optical characteristics under high temperature conditions such as 200 ° C. to 300 ° C. in the solder reflow process. Therefore, it can be suitably used for an infrared cut filter that is mounted on an imaging optical device that requires high productivity in manufacturing.

Claims

The cured resin composition has absorption over the entire wavelength range of 700 to 1100 nm,
Before and after the reflow test in which the operation of holding at 260 ° C. for 60 seconds and then cooling to room temperature is repeated three times, the average light transmittance at 400 to 600 nm in the cured resin composition is 50% or more, and 750 to 850 nm. A curable resin composition having an average transmittance of 20% or less and a change rate of transmittance at a wavelength of 750 nm within ± 5%.
The curable resin composition of Claim 1 containing a curable composition (A) and a near-infrared absorption compound (B).
A near-infrared absorbing material obtained using the curable resin composition according to claim 2,
A near-infrared absorbing compound (B-2) is contained on the surface of a molded product obtained from a transparent resin composition containing the curable composition (A) and a nonionic infrared absorbing compound (B-1). A near-infrared absorbing material having a layer to perform.
The curable composition (A) is at least one selected from the group consisting of a curable silicone composition, a curable epoxy silicone composition, a curable acrylic composition, a curable norbornene composition, and a curable polyimide composition. The near-infrared absorbing material according to claim 3, which is a seed.
The curable composition (A) is
(A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule;
(B) a hydrosilylation catalyst;
(C) an organosiloxane compound containing at least two SiH groups in one molecule;
The near-infrared absorption material of Claim 3 or 4 which contains as an essential component.
The nonionic infrared absorbing compound (B-1) is contained in an amount of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the curable composition (A). Near-infrared absorbing material.
The near-infrared ray according to any one of claims 3 to 6, wherein the nonionic near-infrared absorbing compound (B-1) is at least one selected from the group consisting of perylene compounds and quatarylene compounds. Absorbing material.
The near-infrared absorbing material according to any one of claims 3 to 7, wherein the near-infrared absorbing compound (B-2) is a composite tungsten oxide compound.
The near-infrared absorbing material according to claim 8, wherein the layer containing the composite tungsten oxide compound has a thickness in a range of 0.1 µm to 10 µm.
The near-infrared absorbing material according to claim 8 or 9, wherein the composite tungsten oxide compound is a cerium-containing composite tungsten oxide.
A method for producing a near-infrared absorbing material according to any one of claims 3 to 9,
A solution in which the near-infrared absorbing compound (B-2) is dispersed so as to be 1 to 50 parts by weight with respect to 100 parts by weight of the organic solvent is prepared,
A near-infrared absorbing material for applying the solution to the surface of a molded product obtained from a transparent resin composition containing a curable composition (A) and a nonionic infrared absorbing compound (B-1). Production method.
The coating is performed by at least one of spin coating, casting, micro gravure coating, gravure coating, knife coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. The manufacturing method of the near-infrared absorption material of Claim 11 performed by using.
An aliphatic hydrocarbon solvent selected from hexane and heptane; an aromatic hydrocarbon solvent selected from anisole, mesitylene, toluene, and xylene; a ketone solvent selected from methyl isobutyl ketone, cyclohexanone, and acetone; An ether solvent selected from tetrahydrofuran, dioxolane, and dioxane; an amide solvent selected from 1-methyl-2-pyrrolidinone, dimethylacetamide, and dimethylformamide; and at least one selected from the group consisting of silicon solvents. A method for producing a near infrared ray absorbing material according to 11 or 12.
A curable coating agent comprising the curable resin composition according to claim 2,
As the near-infrared absorbing compound (B), at least one selected from the group consisting of complex tungsten oxide compounds, phthalocyanine compounds, and naphthalocyanine compounds, and at least selected from the group consisting of perylene compounds and quatarylene compounds One type of curable coating agent.
The curable coating agent according to claim 14, wherein the composite tungsten oxide compound is a cesium-containing tungsten oxide.
Further comprising a solvent (C),
Contains 0.01 to 100 parts by weight of the near-infrared absorbing compound (B) and higher than 0 parts by weight and 1000 parts by weight or less of the solvent (C) with respect to 100 parts by weight of the curable composition (A). The curable coating agent according to claim 14 or 15.
The curable composition (A) is at least one selected from the group consisting of a curable silicone composition, a curable epoxy silicone composition, a curable acrylic composition, a curable norbornene composition, and a curable polyimide composition. The curable coating agent according to claim 16, wherein
The curable composition (A) is
(A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule;
(B) a hydrosilylation catalyst;
(C) an organosiloxane compound containing at least two SiH groups in one molecule;
The curable coating agent of Claim 16 or 17 which contains as an essential component.
Solvent (C) is hexane, heptane, anisole, mesitylene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, tetrahydrofuran, dioxolane, dioxane, 1-methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide, and silicon The curable coating agent according to any one of claims 16 to 18, which is at least one selected from the group consisting of a system solvent.
A near-infrared absorbing material obtained by applying the curable coating agent according to any one of claims 14 to 19 to at least one surface of a transparent substrate, evaporating the solvent, and then curing.
A curable composition comprising the curable resin composition according to claim 2,
(A) an organic compound having at least two carbon-carbon double bonds reactive with SiH groups in one molecule;
(B) a hydrosilylation catalyst;
(C) a compound containing at least two SiH groups in one molecule;
(D) a near-infrared absorbing composition comprising a quatarylene compound and at least one compound selected from a phthalocyanine compound and a naphthalocyanine compound;
A curable composition containing
The component (a) is represented by the following general formula (IV)

(Wherein R 3 has a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R 3 may be different or the same, and at least two R 3 may be SiH Including carbon-carbon double bonds that are reactive with groups)
The curable composition of Claim 21 which is an organic compound represented by these.
The component (a) is represented by the following general formula (III)

(Wherein R 4 represents a monovalent organic group having 1 to 50 carbon atoms which may be substituted with oxygen, nitrogen, sulfur or halogen atoms, and each R 4 may be the same even if different. May be.)
The curable composition of Claim 21 which is an organic compound represented by these.
The component (c) is
(Α) an organic compound having at least one carbon-carbon double bond reactive with a SiH group in one molecule;
(Β) a polyorganosiloxane having a chain, cyclic, branched or cage structure having at least three SiH groups in one molecule;
The curable composition according to any one of claims 21 to 23, which is a compound obtained by hydrosilylation reaction.
The component (α) is represented by the following general formula (IV)

(Wherein R 3 represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R 3 may be different or the same, and at least one R 3 is a SiH group. Including carbon-carbon double bonds that are reactive with
The curable composition of Claim 24 which is an organic compound represented by these.
The component (α) is represented by the following general formula (III)

(Wherein R 4 represents a monovalent organic group having 1 to 50 carbon atoms which may be substituted with oxygen, nitrogen, sulfur or halogen atoms, and each R 4 may be the same even if different. May be.)
The curable composition of Claim 24 which is an organic compound which has a structure represented by these.
As the component (β), the following general formula (VI)

(Wherein R 14 and R 15 each independently represents an organic group having 1 to 10 carbon atoms, n represents 3 to 10, and m represents a number of 0 to 10).
The curable composition according to any one of claims 24 to 26, which comprises a compound represented by:
A cured product obtained by curing the curable composition according to any one of claims 21 to 27.
An optical material comprising the near-infrared absorbing material according to any one of claims 3 to 10 and 20, or the cured product according to claim 28 as an infrared shielding body.