JP2005239999A - Resin composition for forming visible light, near infrared ray or neon light absorbing layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition which can reconcile both of the durability of a pigment and bending properties, is improved in the stability of the pigment in the resin liquid, and can form a layer capable of absorbing at least one kind of visible light, near infrared rays, and neon light. <P>SOLUTION: The resin composition is used for forming the layer capable of absorbing at least one of visible light, near infrared light and neon light, and contains the pigment having the maximum absorption wavelength in 380-1200 nm and a polymer containing lactone rings, N-substituted maleimide rings or tetrahydropyran rings. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a resin composition used for forming a layer that absorbs at least one of visible light, near infrared light, and neon light. More specifically, the present invention relates to a resin composition used for forming a layer that reduces transmission of light having a specific wavelength such as visible light, near infrared light, or neon light in various fields such as a plasma display panel (PDP).

In general, plasma display panels (PDPs) generate electromagnetic waves that are said to affect the human body, near infrared rays that cause malfunctions of the remote control, neon light that reduces color reproducibility, and the like. In order to reduce this, a filter is installed in front of it. As a front filter, what is comprised from the resin composition containing the compound and binder resin which can absorb these lights, etc. are mentioned, for example.

In the resin composition constituting such a front filter, for example, heat may be generated by operating a plasma display panel, or it may be manufactured, transported or used in a place with high humidity. Durability such as heat resistance and heat-and-moisture resistance is required so that the effect of reducing the transmission of light having a specific wavelength due to deterioration due to the deterioration is not required. Furthermore, in the process of manufacturing such a front filter, for example, it is often applied to a substrate such as a film of polyethylene terephthalate (PET) and wound around a roll or the like. There is a need for a resin composition that can form a flexible coating film that can sufficiently withstand such deformation.

However, when a compound capable of absorbing light having a specific wavelength is added to the resin composition constituting the front filter, durability such as heat resistance and moisture heat resistance in the coating film of such a compound. In order to improve the property, a binder resin having a high glass transition temperature (Tg) is preferred. However, if the binder resin has a high Tg, the flexibility of the coating film is not sufficient and cracks are likely to occur. For this reason, there was room for improvement in making the resin composition compatible with both durability and flexibility.

Conventionally, in an optical film using a dye having a maximum absorption wavelength in the visible range or near infrared range of 380 to 1200 nm, a binder containing a dye for improving the stability of the dye in a heat resistance test and a moist heat resistance test An optical film using an acrylic resin having a specific glass transition temperature (abbreviated as Tg) has been proposed. For example, it has been proposed that the use of a resin that usually contains 50% by weight or more of an acrylic resin having a Tg of 110 ° C. or higher improves the stability of the dye in a heat resistance test and a light resistance test (for example, Patent Literature 1). However, in the coating film prepared using the disclosed acrylic resin having a Tg of 110 ° C. or higher containing 50% by weight or more, the coating film is hard and brittle, so that the coating film is cracked in the manufacturing process. It was easy and difficult to industrially produce an optical film using the binder. Also, when preparing optical films, paints containing pigments and binders are prepared. However, paints formulated with such acrylic resins as binders are prone to inactivation of pigments in the blended solution, and the paint can be used. There was a time limit.

The near-infrared-absorbing coating film contains a near-infrared-absorbing dye having a maximum absorption wavelength at 780 nm to 1200 nm, and the near-infrared-absorbing ability remaining rate after 48 hours of light irradiation in an accelerated weather resistance test using an ultraviolet autofade meter is 50. % Is disclosed (see Patent Document 2).
Such a coating film contains a near-infrared absorbing dye and is excellent in light resistance, but also has excellent dye durability even when a dye having a maximum absorption wavelength in the wavelength range of visible light or neon light is used. There was room for the device to be a coating film having

By the way, the photosensitive resin composition containing the lactone ring containing polymer obtained from the monomer component containing 2- (hydroxyalkyl) acrylic acid ester and the monomer which has an acid group (for example, refer patent document 3), 2 A lactone ring-containing polymer obtained from a monomer component containing-(hydroxyalkyl) acrylic acid ester and a monomer having an acid group and having a radically polymerizable double bond in the side chain (see, for example, Patent Document 4). Is disclosed. These compositions and the like are useful, for example, as a photoresist material that is coated on a substrate, cured by being irradiated with ultraviolet rays through a photomask, and then developed with an alkaline solution. However, these compositions and the like are different in technical field from resin compositions and the like used for front filters and optical films of plasma displays. That is, it is not intended to reduce the transmission of near-infrared rays and the like, and there is room for improvement in characteristics such as flexibility required for constituting a front filter and an optical film.

Further, it is obtained by copolymerizing a composition containing 20 to 98% by weight of maleimide monomer and methyl methacrylate, and the total weight ratio of maleimide monomer and methyl methacrylate is 30% by weight or more. And an optical resin plate having a refractive index of 1.520 ± 0.020 (see Patent Document 5), a binder resin, a dye, a dispersant, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. , A photosensitive coloring composition (see Patent Document 6), which is a copolymer containing a monomer having an N-substituted maleimide and an acid group as a binder resin, a polymerizable dye having a specific structure containing a nitrogen atom, and N-phenyl A colored composition using a colored copolymer in which the polymerization ratio of a copolymer obtained by polymerizing maleimide and another monomer is 3 to 40% by weight of N-phenylmaleimide with respect to 100% by weight of the copolymer ( Patent Document 7 reference.) Is disclosed.
However, these compositions and the like are not intended to reduce transmission of near-infrared rays and the like, and there is room for improvement that can be suitably used for a front filter or an optical film of a plasma display. It was.

Conventionally used binder resins for front filters include PC (polycarbonate resin), O-PET (trade name, manufactured by Kanebo Corp., fluorene polyester), etc., but these are solvent-soluble and coating work. Since the properties, paint stability and the like are not sufficient, acrylic resins and the like disclosed in Patent Document 1 and Patent Document 2 described above have been studied as alternative resins.

By the way, the front filter is provided on the surface of the plasma display via an air layer (space layer), but in the next generation plasma display, the front filter is directly pasted on the display in order to improve sharpness. To be considered. However, since the plasma display often has a high temperature of 80 ° C. or higher, the binder resin used for the front filter is required to have higher heat resistance and moisture heat resistance than before. For example, when a front filter is provided via an air layer, heat resistance at 80 ° C. and moisture heat resistance at 60 ° C. and 95% RH are required, but when directly attached, heat resistance at 100 ° C. and 80 ° C. Moist heat resistance at 95% RH is required. In addition, for example, solubility in solvents, coating workability, flexibility (flexibility) when used as a coating film, paint stability when mixed with a pigment, etc. are required, and in terms of cost. However, an inexpensive one is desired. In such next-generation plasma displays, high levels of heat resistance and heat-and-moisture resistance cannot be achieved even with conventional acrylic resins, so they exhibit higher thermal characteristics and satisfy various required performances. What can be done is sought.
JP2003-167119A (pages 2-3 and 5-6) JP 2002-249721 A (2nd page) JP 2002-303975 A (page 2) JP 2002-356520 A (2nd page) Japanese Patent Laid-Open No. 6-194501 (2nd page) JP-A-10-31308 (2nd page) JP 2001-11336 A (page 2-3)

The present invention has been made in view of the above situation, and can achieve both the durability of the pigment and the flexibility of the coating film, and the stability of the pigment in the resin liquid is improved. It aims at providing the resin composition which can form the layer which absorbs at least 1 sort (s) among infrared rays and neon rays.

The inventors of the present invention have made various studies on a resin composition that can form a layer that reduces transmission of near infrared rays and the like. Paying attention to being useful for the formation of front filters and optical films used in display panels, and having a maximum absorption wavelength at 380 to 1200 nm as a dye, light having a specific wavelength such as near infrared It has been found that it can be sufficiently absorbed, and has a lactone ring, an N-substituted maleimide ring or a tetrahydropyran ring as a binder resin, thereby improving durability such as heat resistance and moist heat resistance in the dye. And found that the flexibility of the coating film can be fully exhibited. And a resin composition that forms a layer capable of sufficiently reducing transmission of light having a specific wavelength such as near infrared by combining such a dye with a polymer containing a lactone ring, an N-substituted maleimide ring, or a tetrahydropyran ring. The inventors have found that it can be made suitable as a product, and have come up with the idea that the above problems can be solved brilliantly. Furthermore, it has been found that the storage stability of the dye in the resin liquid can be improved by using such a combination, and the present invention has been achieved.
Thus, a polymer having a lactone ring, an N-substituted maleimide ring, or a tetrahydropyran ring is used as a binder for blending a dye having a maximum absorption wavelength in the visible range, near infrared range of 380 to 1200 nm, or the wavelength range of neon light. Then, in spite of the high Tg coating film, the coating film is excellent in flexibility, so that even if the optical film using the binder is folded, the coating film is hardly cracked. In addition, in the heat resistance test and the moist heat resistance test, the deterioration of the dye is very small. Furthermore, in the paint containing the binder, there is little deterioration of the pigment, and the usable life of the paint can be long.

That is, the present invention is a resin composition used for forming a layer that absorbs at least one of visible light, near infrared light, and neon light, and the resin composition has a maximum absorption wavelength at 380 to 1200 nm. A resin composition comprising a dye and a polymer containing a lactone ring, an N-substituted maleimide ring or a tetrahydropyran ring.
The present invention is described in detail below.

The resin composition of the present invention contains a dye having a maximum absorption wavelength within the above wavelength range and a binder resin essentially comprising a lactone ring, an N-substituted maleimide ring or a tetrahydropyran ring-containing polymer, and is visible. Any layer that can reduce the transmission of light including at least one of light, near infrared, and neon light may be used. In addition, the component contained in the resin composition of this invention can use 1 type (s) or 2 or more types, respectively.
The binder resin is not particularly limited as long as it has a polymer having at least one of a lactone ring, an N-substituted maleimide ring, and a tetrahydropyran ring. For example, the binder resin has three types of rings. In the case of containing a polymer, it may contain a polymer having both a lactone ring, an N-substituted maleimide ring and a tetrahydropyran ring, or a polymer containing a lactone ring, an N-substituted maleimide ring-containing polymer, And a mixture (blend) with a tetrahydropyran ring-containing polymer. In the case of containing a polymer having two kinds of rings, it may contain a polymer having both of the two kinds of rings, or may contain a mixture of polymers having respective rings. Also good.

The dye having the maximum absorption wavelength at 380 to 1200 nm may be any compound having the maximum absorption wavelength in the above-mentioned wavelength range. For example, as a dye having the maximum absorption wavelength at 380 to 780 nm, JP-A-2002-200711 Cyanine dyes represented by the formulas (6), (7) and (8) described in the publication; tetraazaporphyrin-based dyes represented by the general formula (I) described in JP-A-2003-36033; Pyrazolylmethine dye, dipyrazolyl squarylium dye represented by the general formula (III); other cyanine, azurenium, squarylium, diphenylmethane, triphenylmethane, oxazine, azine, thiopyrylium, viologen, azo , Azo metal complex, bisazo, anthraquinone, perylene, Dansuron based, nitroso-based, metal-thiol complex dyes, indigo dyes, azomethine dyes, xanthene dyes, oxanol type, indoaniline, can be widely used quinoline, etc. conventionally known dyes. More specifically, for example, “Adeka Arcles TW-1367”, “Adeka Arkles SG-1574”, “Adeka Arkles TW1317”, “Adeka Arkles FD-3351”, “Adeka Arkles Y944” (all products) “NK-5451”, “NK-5532”, “NK-5450” (all trade names, manufactured by Hayashibara Biochemical Laboratories) and the like are suitable.

Moreover, as a pigment | dye which has maximum absorption wavelength in 780-1200 nm, the phthalocyanine compound shown by Formula (1) of Unexamined-Japanese-Patent No. 2001-106869; Fragrance shown by General formula (1) of Unexamined-Japanese-Patent No. 2002-82219 Group dithiol-based metal complexes, aromatic diimmonium compounds represented by general formulas (2) and (3), aromatic diol compounds represented by general formulas (4) to (9); diimonium-based compounds described in JP-A-2001-133624 Compound: Other nitroso compound and its metal complex salt, cyanine compound, thiol nickel complex compound, dithiol nickel complex compound, aminothiol nickel complex compound, phthalocyanine compound, naphthalocyanine compound, triallylmethane compound, Imonium compounds, diimonium compounds, naphtho Emissions-based compounds, anthraquinone compounds, amino compounds, aminium salt compound, and an organic substance such as squarylium compound and a methine-based compounds other than those described above; antimony-doped tin oxide, indium-doped tin oxide and the like.

As content of the pigment | dye which has maximum absorption wavelength in said 380-1200 nm, it is preferable that a lower limit is 0.0005 mass% with respect to the non volatile matter of the resin composition of this invention. When it is less than 0.0005% by mass, there is a possibility that light having a specific wavelength cannot be sufficiently absorbed when a coating film is formed. More preferably, it is 0.0015 mass%. As an upper limit, it is preferable that it is 20 mass%. If it exceeds 20% by mass, the basic performance such as the strength of the coating film and the durability of the dye may not be sufficiently improved. More preferably, it is 15 mass%, More preferably, it is 10 mass%.

The lactone ring-containing polymer may be a polymer containing a ring structure having an ester group (—CO—O—) in the ring, and even if it has a lactone ring in the main chain, Preferably, it has a lactone ring in the main chain. Having in the main chain is a form incorporated as a part of the main chain, and the main chain means a part of a chain formed by combining repeating units (monomer units). Having in the side chain means being a part of the side chain, and the side chain means a part of the chain branched from the main chain.

Examples of the lactone ring-containing polymer include the following general formula (1);

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may have oxygen). A polymer having the structural unit represented is preferable. By having such a structure, the effects of the present invention can be sufficiently exhibited.
Examples of the organic residue having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 20 carbon atoms, and an aromatic group having 1 to 20 carbon atoms. Etc.

The N-substituted maleimide ring-containing polymer includes a heavy structure containing a ring structure having one N-substituted imide group (—CO—NR—CO—, R is a monovalent substituent) sandwiched between two carbonyl groups. It may be a combination, and may have an N-substituted maleimide ring in the main chain or a side chain, but preferably has an N-substituted maleimide ring in the main chain.
The N-substituted maleimide ring-containing polymer has the following general formula (4):

(Wherein R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group. R ⁹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group. It is preferably a polymer having a structural unit represented by:

R ⁹ is, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, an octyl group, or an octadecyl group; a branched alkyl group such as an isopropyl group, a sec-butyl group, a tert-butyl group, or an isopentyl group. A cycloalkyl group such as a cyclohexyl group or a methylcyclohexyl group; an aryl group such as a phenyl group or a methylphenyl group; an aralkyl group such as a benzyl group or a phenethyl group;

The tetrahydropyran ring-containing polymer may be a polymer containing a 6-membered ring structure having an ether bond, and even if it has a tetrahydropyran ring in the main chain, it has a side chain. However, it preferably has a tetrahydropyran ring in the main chain.
The tetrahydropyran ring-containing polymer has the following general formula (5):

(Wherein R ¹⁰ and R ¹¹ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, an alicyclic hydrocarbon group or a substituted hydrocarbon group). It is preferable that it is a polymer which has.

R ¹⁰ and R ¹¹ are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2- Linear or branched alkyl group such as ethylhexyl group; aryl group such as phenyl group; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, An alicyclic group such as an adamantyl group and 2-methyl-2-adamantyl group; an alkyl group substituted with alkoxy such as 1-methoxyethyl group and 1-ethoxyethyl group; an alkyl substituted with an aryl group such as benzyl group; Groups etc. are preferred.
Among these, a primary or secondary carbon substituent which is difficult to be removed by an acid or heat such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group is preferable from the viewpoint of heat resistance.

As content of the said lactone ring, N substituted maleimide ring, or tetrahydropyran ring containing polymer, when the resin composition of this invention is 100 mass% in conversion of a non volatile matter, it is preferable that a lower limit is 20 mass%. If it is less than 20% by mass, the durability of the dye may not be sufficiently improved. More preferably, it is 40 mass%, More preferably, it is 70 mass%. The upper limit is preferably 99.9995% by mass. If it exceeds 99.9995% by mass, there is a possibility that light having a specific wavelength in the case of a coating film cannot be sufficiently absorbed. More preferably, it is 99.9985 mass%, More preferably, it is 99.99 mass%.

As a method for producing the lactone ring-containing polymer, for example, a polymer is obtained by polymerizing monomer components, and lactone cyclization is performed by cyclizing condensation of functional groups that the polymer has. (1) a method of performing cyclization condensation together with polymerization of the monomer component, (2) after obtaining the polymer (a) by polymerizing the monomer component, the polymer The method etc. which perform the cyclization condensation of (a) can be mentioned. It can also be produced by (3) a method of polymerizing a monomer having a lactone ring as a monomer component. In addition, about the raw material etc. which are used for this manufacturing method, 1 type (s) or 2 or more types can each be used.
The lactone cyclization refers to a polymer (for example, a polymer) obtained by cyclizing and condensing a hydroxyl group formed in a polymer obtained by polymerizing monomer components, a carboxyl group, an ester group, or the like. In the main chain) to form a lactone ring structure. Water and alcohol are by-produced by lactone cyclization.

As said monomer component, what is necessary is just to contain the monomer which can form the functional group which can be lactone cyclized in a polymer, for example, following General formula (2);

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms). It is. The organic residue having 1 to 20 carbon atoms is the same as described above.

Examples of the monomer represented by the general formula (2) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- 2- (Hydroxyalkyl) acrylic acid esters such as n-butyl (hydroxymethyl) acrylate, tert-butyl 2- (hydroxymethyl) acrylate, 2-ethylhexyl 2- (hydroxymethyl) acrylate are preferred, and these Of these, methyl 2- (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred. These may be used alone or in combination of two or more.

The content of the monomer represented by the general formula (2) is preferably 5% by mass as the lower limit when the total monomer component of the lactone ring-containing polymer is 100% by mass. . If it is less than 5% by mass, since the lactone ring structure is small, the Tg of the coating film becomes low, and the dye in the heat resistance test and moist heat resistance test tends to deteriorate. Moreover, in the paint which mix | blended the said binder, deterioration of a pigment | dye is easy and there exists a possibility that the usable time of a paint may become short. More preferably, it is 10 mass%. The upper limit is preferably 70% by mass. If it exceeds 70% by mass, a lactone cyclization reaction occurs in the molecule, and thus gelation tends to occur, and a lactone ring-containing polymer may not be obtained. More preferably, it is 50 mass%.

In the present invention, in order to further improve the durability of the dye in the coating film, such as heat resistance and heat-and-moisture resistance, or to further improve the stability of the dye in the resin liquid, a monomer containing a fluorine atom And / or the following general formula (3);
^{_{CH 2 = C (R 6)}} CO-OX (3)
(In the formula, R ⁶ represents a hydrogen atom or a methyl group. X represents a hydrocarbon group having 4 to 25 carbon atoms.) preferable.

As the monomer containing a fluorine atom, for example, a radical polymerizable monomer having a perfluoroalkyl group or a perfluoroether group is suitable, and examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoromethyl group, and a perfluoroalkyl group. A fluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluorododecyl group, perfluorotetradecyl group and the like are preferable.

As such a monomer containing a fluorine atom, CH ₂ ═C (CH ₃ ) COOCH ₂ (CF ₂ ) ₄ CF ₃ , CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ CF ₃ , CH ₂ ═CHCOO (CF ₂ ) ₆ CF ₃ , CH ₂ ═CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ , CH ₂ ═CHCOOCH ₂ CH ₂ (CF ₂ ) ₅ CF (CF ₃ ) ₂ , CH _{2 = C (CH 3) COOCH (} OCOCH 3) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CHCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 _{= CHCOOCH 2 CH 2 (CF 2} ) 8 CF 3, CH 2 = C (CH 3) COOCH 2 CH 2 NHCO (CF 2) 8 CF 3, CH 2 = CHO CONHCO (CF ₂ ) ₇ CF (CF ₂ Cl) CF ₃ , CH ₂ ═CHCOOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ (CF ₂ ) ₇ CF ₃ , CH ₂ ═CHCOOCH ₂ CH ₂ CH ₂ CH _{2 (CF 2) 7 CF 3,} CH 2 = C (CH 3) COOCH 2 CH 2 N (C 2 H 5) SO 2 (CF 2) 7 CF 3, CH 2 = CHCOOCH 2 CH 2 NHCO (CF 2) 7 CF ₃ , CH ₂ = CHCOO (CH ₂ ) ₃ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₀ H, CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) _{10 CF 2 Cl, CH 2 =} CHCONHCH 2 CH 2 OCOCF (CF 3) OC 3 F 7, CH 2 = CHCONHCH 2 CH 2 OCOC _{(CF 3) (OC 3 F} 6) 2 OC 3 F 7 is preferred. A commercial item can also be used as a monomer containing a fluorine atom. For example, “Light Ester FM-108”, “Light Ester M-3F”, “Light Ester M-4F” (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.); “CHEMINOX FAAC”, “CHEMINOX FAMAC”, “CHEMINOX FAAC” -M "," CHEMINOX FAMAC-M "," CHEMINOX PFAE "," CHEMINOX PFOE "(all trade names, manufactured by Nippon Mektron) are suitable.

As content of the said monomer containing a fluorine atom, when all the monomer components shall be 100 mass%, it is preferable that it is 5 mass% as a lower limit. If it is less than 5% by mass, the dye in the heat resistance test and moist heat resistance test may be easily deteriorated. Moreover, in the paint which mix | blended the said binder, deterioration of a pigment | dye is easy and there exists a possibility that the usable time of a paint may become short. More preferably, it is 10 mass%. As an upper limit, it is preferable that it is 50 mass%. If it exceeds 50% by mass, the coating film tends to be softened, and the resin becomes expensive and may not be practically usable. More preferably, it is 20 mass%.

In the monomer represented by the general formula (3), examples of the hydrocarbon group having 4 to 25 carbon atoms represented by X include fats such as a cyclohexyl group, a methylcyclohexyl group, and a cyclododecyl group. Cyclic hydrocarbon group; straight chain such as butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, octadecyl group or the like A branched alkyl group; a polycyclic hydrocarbon group such as bornyl group and isobornyl group is preferred. Among these, an alicyclic hydrocarbon group, a branched alkyl group, a linear alkyl group having 6 or more carbon atoms, and a polycyclic hydrocarbon group are preferable. More preferred are an alicyclic hydrocarbon group having 6 or more carbon atoms and a polycyclic hydrocarbon group.

Examples of the monomer represented by the general formula (3) include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, JP 2002-69130 A Cyclohexyl alkyl esters of (meth) acrylic acid, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl ( Data) acrylate, tricyclo [5,2,1,0 ^2.6] dec-8-yl (meth) acrylate and the like.

The content of the monomer represented by the general formula (3) is preferably 5% by mass as the lower limit when the total monomer component of the lactone ring-containing polymer is 100% by mass. . If it is less than 5% by mass, the dye in the heat resistance test and moist heat resistance test may be easily deteriorated. Moreover, in the paint which mix | blended the said binder, deterioration of a pigment | dye is easy and there exists a possibility that the usable time of a paint may become short. More preferably, it is 10 mass%. The upper limit is preferably 60% by mass. If it exceeds 60% by mass, the flexibility of the coating film may be lowered. More preferably, it is 40 mass%.

Other copolymerizable unsaturated monomers that can be used in addition to the above monomer components include unsaturated monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic anhydride; 2 -Acid phosphate ester unsaturated monomers such as (meth) acryloyloxyethyl acid phosphate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy ( Unsaturated monomer having a group having active hydrogen such as (meth) acrylate (for example, trade name “PLAXEL FM” manufactured by Daicel Chemical Industries, Ltd.); methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) (Meth) acrylic acid such as acrylate and isopropyl (meth) acrylate Ester; glycidyl (meth) unsaturated monomer having a epoxy group, such as acrylate are preferred.

Furthermore, unsaturated monomers having a nitrogen atom such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, imide (meth) acrylate, cyclohexylmaleimide; ethylene Two or more polymerizable dimers such as glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Unsaturated monomer having a heavy bond; Unsaturated monomer having halogen atom such as vinyl chloride (excluding the above-mentioned monomer containing fluorine atom); Aromatic unsaturated monomer such as styrene and α-methylstyrene Vinyl ester such as vinyl acetate; vinyl Ether and the like can also be used.

If it is necessary to further improve the durability of the dye, use an unsaturated monomer having a UV-absorbing group such as benzotriazole, benzophenone, or triazine (polymerizable UV-absorbing monomer). That's fine. Specific examples include “RUVA93” (trade name, manufactured by Otsuka Chemical Co., Ltd.), “BP-1A” (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), and the like. In addition, as an unsaturated monomer having a UV-stable group (polymerizable UV-stable monomer), “ADK STAB LA-82” and “ADK STAB LA-87” (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Examples of the unsaturated monomer having an antioxidant ability (polymerizable antioxidant monomer) include “Sumilyzer GS” and “Sumilyzer GM” (both trade names, manufactured by Sumitomo Chemical Co., Ltd.).
In addition, the durability of the dye can be further improved by adding a quencher to the resin composition of the present invention. As such a quencher, for example, “CIR1080”, “CIR1081”, “CIR960” (all trade names, manufactured by Nippon Carlit Co., Ltd.), trade names “MIR101” manufactured by Midori Chemical Co., Ltd., manufactured by Sumitomo Seika Co., Ltd. An example of the product name is “EST5”.

As the method (1) in the method for producing the lactone ring-containing polymer, for example, a method of subjecting a monomer component to solution polymerization is suitable. That is, by using a solvent capable of sufficiently dissolving the obtained lactone ring-containing polymer, solution polymerization of the above-described monomer components allows the monomer having an acid group or the lactone ring-containing polymer to be obtained. It acts as a catalyst for cyclization and can be lactone cyclized together with copolymerization of monomer components. Further, if necessary, a known transesterification catalyst or esterification catalyst may be used as the lactone cyclization catalyst. From the viewpoint of reducing the coloration of the coating film, the organic compounds disclosed in JP-A-2001-151814. Phosphorus compounds are preferred.

As a method for charging the monomer component, (a) the whole amount may be charged all at once, (b) a part may be charged all at once and the rest may be dropped, or (c) the whole amount is dropped. The form (b) or (c) is preferable from the viewpoint of controlling the calorific value.
The reaction temperature for the solution polymerization is preferably 50 to 200 ° C., and may be refluxed at the boiling point of the solvent.

As the solvent used in the solution polymerization, those used in usual radical polymerization reaction can be used, for example, ethers such as diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; Preference is given to esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; alcohols such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene and xylene.

In the polymerization, if necessary, a polymerization initiator that is usually used may be used. For example, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, organic peroxides such as t-butylperoxy-2-ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 2,2′- Azo compounds such as azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) are preferred.
What is necessary is just to set suitably as the usage-amount of the said polymerization initiator according to the combination of the monomer to be used, reaction conditions, etc. Moreover, it does not restrict | limit especially also as the injection | throwing-in method of a polymerization initiator, The whole quantity may be charged collectively, a part may be charged collectively, the remainder may be dripped, and the whole quantity may be dripped. It is preferable to add it together with the monomer component because the reaction can be easily controlled, and it is preferable to add it after the monomer component addition because the residual monomer can be reduced.
In the case of the above polymerization, a chain transfer agent that is usually used may be added as necessary to adjust the molecular weight, such as a thiol chain transfer agent such as n-dodecanethiol, α-methylstyrene dimer, etc. Is preferred.

In the above polymerization, it is preferable to perform aging as necessary after adding the monomer component, the polymerization initiator, and the chain transfer agent. Moreover, it is preferable to perform operation for dehydration and dealcoholization after reaction or aging. Thereby, the lactone cyclization rate can be further improved, and the durability of the dye and the flexibility of the coating film can be further improved when the resin composition of the present invention is used.
Examples of the dehydration / dealcoholation method include a method of distilling off at normal pressure or reduced pressure, a method of distilling dry nitrogen or dry argon while bubbling at normal pressure or reduced pressure, and toluene or cyclohexane at normal pressure or reduced pressure. A method of azeotroping with them is preferred. In this case, the amount of remaining water / alcohol is preferably 1% by mass or less based on the entire reaction solution. More preferably, it is 0.3 mass% or less, More preferably, it is 0.1 mass% or less.

The method (2) is a method for producing a lactone ring-containing polymer by polymerizing monomer components to obtain a polymer (a) and then cyclizing the polymer (a).
As a polymerization method for obtaining the polymer (a), solution polymerization or bulk polymerization is preferable, and solution polymerization is more preferable.
What is necessary is just to set suitably as the said polymerization temperature and polymerization time according to the kind of monomer component to be used, a ratio, etc., and it is preferable that they are polymerization temperature 0-200 degreeC and polymerization time 0.5-20 hours.

When the polymer (a) is obtained by solution polymerization, the polymerization reaction mixture contains a solvent in addition to the obtained polymer (a). The polymer (a) ) In the solid state, and it is preferable to carry out the lactone cyclization reaction in a state containing the solvent. Further, if necessary, a solvent suitable for the lactone cyclization reaction may be added again after taking it out as a solid. Moreover, also when obtaining a polymer (a) by another polymerization method, a solvent may be added after superposition | polymerization as needed, and after taking out as a solid, a solvent may be added.
The reaction solvent used when the polymer (a) is obtained by polymerization is the same as that described above.

About the manufacturing method of the said lactone ring containing polymer, although a lactone cyclization rate is measured by the dealcoholization reaction rate mentioned later, it is preferable that it is 80% or more by this dealcoholization reaction rate. More preferably, it is 85% or more, and still more preferably 90% or more. If the lactone cyclization rate is low, the amount of residual hydroxyl groups increases, and the stability of the paint blended with the dye may decrease, or the stability of the dye may decrease due to the low Tg of the resulting coating film. .

As a glass transition temperature (Tg) of the said lactone ring containing polymer, it is preferable that a lower limit is 90 degreeC. If it is lower than 90 ° C., the dye may be easily deteriorated in a heat resistance test and a moist heat resistance test. More preferably, it is 100 degreeC. The upper limit is preferably 210 ° C. When it exceeds 210 degreeC, there exists a possibility that coating workability | operativity may worsen and the finishing external appearance of a coating film may worsen. More preferably, it is 200 degreeC.
As a method for measuring the glass transition temperature, for example, the obtained polymer solution is put into excess n-hexane to perform reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (133 Pa), 80 ° C., 3 hours or more), volatile components and the like can be removed, and the obtained white solid resin can be measured using a DSC (Differential Scanning Calorimeter) device.

The acid value per gram of the lactone ring-containing polymer is preferably 0 to 20 mgKOH / g. More preferably, it is 0-10 mgKOH / g. When the acid value exceeds 20 mgKOH / g, the dye in the heat resistance test and the moist heat resistance test may be easily deteriorated. Moreover, there exists a possibility that adhesion | attachment with a plastic base material may fall by a moist heat resistance test. Furthermore, in a paint containing the binder, the pigment is likely to deteriorate, and the usable time of the paint may be shortened.

The acid value can be measured, for example, as follows.
To 0.5 to 1 g of a lactone ring-containing polymer solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and titration is performed using an automatic titrator using a 0.1 mol / L KOH aqueous solution as a titrant. To do. On the other hand, a solution obtained by adding 2 ml of acetone to 0.3 g of a lactone ring-containing polymer solution was naturally dried at room temperature and further dried under reduced pressure (140 ° C./667 Pa (5 mmHg)) for 3 hours in a desiccator. Allow to cool and measure mass. Thereafter, in the same manner as described above, acetone is added and dissolved, and the operation of measuring the mass by natural drying and drying under reduced pressure is repeated until the mass becomes constant, and the nonvolatile content of the solution of the lactone ring-containing polymer is determined from the mass reduction amount. The acid value per 1 g of solid of the lactone ring-containing polymer is calculated from the above titration results.

The lower limit of the weight average molecular weight of the lactone ring-containing polymer is preferably 50,000. If it is less than 50,000, the flexibility of the coating film may be lowered. More preferably, it is 100,000, and more preferably 150,000. The upper limit is preferably 1 million. If it exceeds 1,000,000, the coating workability may be reduced. More preferably, it is 500,000, and more preferably 300,000. A weight average molecular weight can be calculated | required by the molecular weight of polystyrene conversion, for example in GPC (the Tosoh company make, HLC-8120, a column is TSK-GEL GMHXL-L).

As a method for producing the N-substituted maleimide ring-containing polymer, for example, a method of polymerizing a monomer component containing a monomer capable of forming an N-substituted maleimide ring is suitable. Examples of monomers capable of forming a maleimide ring include N-methylmaleimide, Nn-butylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide maleimide, and Nm-methylphenylmaleimide. Np-methylphenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, N -P-methoxyphenylmaleimide, N-o-chlorophenylmaleimide, N- -Chlorophenylmaleimide, Np-chlorophenylmaleimide, N-o-carboxyphenylmaleimide, Nm-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, N-o-nitrophenylmaleimide, Nm-nitrophenylmaleimide , N-p-nitrophenylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, or the like can be used.

The content of the monomer capable of forming the N-substituted maleimide ring is preferably 3% by mass as the lower limit when the total monomer component is 100% by mass. If it is less than 3% by mass, the N-substituted maleimide ring structure is small, so the Tg of the coating film becomes low, and the dye in the heat resistance test and moist heat resistance test may be easily deteriorated. Moreover, in the paint which mix | blended the said binder, deterioration of a pigment | dye is easy and there exists a possibility that the usable time of a paint may become short. More preferably, it is 10 mass%. The upper limit is preferably 70% by mass. When it exceeds 70 mass%, there exists a possibility that durability of a pigment | dye may not fully improve. More preferably, it is 50 mass%.

As the monomer component forming the N-substituted maleimide ring-containing polymer, in addition to the monomer capable of forming the N-substituted maleimide ring, the above-mentioned monomer containing a fluorine atom and / or general It is preferable to contain the monomer represented by Formula (3). Furthermore, the above-mentioned other copolymerizable unsaturated monomer, an unsaturated monomer having an ultraviolet absorbing group, an unsaturated monomer having an ultraviolet stabilizing group, and the like may be contained. The solvent and the initiator are the same as described above. The polymerization temperature and the polymerization time may be appropriately set depending on the type and ratio of the monomer component to be used, and are preferably 50 to 200 ° C. and a polymerization time of 0.5 to 20 hours. It may be refluxed at the boiling point.

As a weight average molecular weight of the said N substituted maleimide ring containing polymer, it is preferable that a lower limit is 50,000. If it is less than 50,000, the flexibility of the coating film may be lowered. More preferably, it is 100,000, and more preferably 150,000. The upper limit is preferably 1 million. If it exceeds 1,000,000, the coating workability may be reduced. More preferably, it is 500,000, and more preferably 300,000. The method for measuring the average molecular weight is the same as that for the lactone ring-containing polymer.

As a method for producing the tetrahydropyran ring-containing polymer, for example, a method of polymerizing a monomer component containing a monomer capable of forming a functional group capable of tetrahydropyran cyclization in the polymer. As such a monomer, for example, the following general formula (6);

(Wherein R ^{12 and} R ¹³ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, an alicyclic hydrocarbon group or a substituted hydrocarbon group). The body is preferred. The hydrocarbon group having 1 to 25 carbon atoms, the alicyclic hydrocarbon group, and the substituted hydrocarbon group are the same as described above.

Examples of the monomer represented by the general formula (6) include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)]. Bis-2-propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2- Propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di ( t-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-pro Noate, di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di ( -Butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (Tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2 , 2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, etc. The above can be used.
Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ' -[Oxybis (methylene)] bis, 2-propenoate, dibenzyl-2,2 '-[oxybis (methylene)] bis-2-propenoate are preferred.

The content of the monomer represented by the general formula (6) is preferably 3% by mass as the lower limit when the total monomer components are 100% by mass. If it is less than 3% by mass, the dye is likely to deteriorate in the paint when the dye is blended, and the usable time of the paint may be shortened. Also, the dye is likely to deteriorate in the heat resistance test and moist heat resistance test. There is a risk. More preferably, it is 5 mass%. The upper limit is preferably 60% by mass. If it exceeds 60% by mass, gelation tends to occur during polymerization, and the flexibility of the coating film tends to decrease. More preferably, it is 40 mass%.
As a monomer component for forming the tetrahydropyran ring-containing polymer, in addition to the monomer capable of forming a functional group capable of cyclization with tetrahydropyran in the polymer, the above-described fluorine atom is used. It is preferable to contain the monomer to contain and / or the monomer represented by General formula (3). In the method for producing a tetrahydropyran ring-containing polymer, in addition to the monomer represented by the general formula (6), a monomer that may be contained in the monomer component, a solvent to be used, an initiator, and polymerization Conditions and the like are the same as in the above-described method for producing the N-substituted maleimide ring-containing polymer.

The lower limit of the weight average molecular weight of the tetrahydropyran ring-containing polymer is preferably 10,000. If it is less than 10,000, the flexibility of the coating film may be lowered. More preferably, it is 20,000. The upper limit is preferably 200,000. If it exceeds 200,000, gelation tends to occur during the polymerization process, and the coating workability may be reduced. More preferably, it is 100,000. The measuring method of a weight average molecular weight is the same as that of the above-mentioned lactone ring containing polymer.

The glass transition temperature (Tg) of the N-substituted maleimide ring-containing polymer or tetrahydropyran ring-containing polymer is preferably 90 ° C. If it is lower than 90 ° C., the dye may be easily deteriorated in a heat resistance test and a moist heat resistance test. More preferably, it is 100 degreeC. The upper limit is preferably 200 ° C. When it exceeds 200 degreeC, there exists a possibility that coating workability | operativity may worsen and the finishing external appearance of a coating film may worsen. More preferably, it is 150 degreeC. The method for measuring the glass transition temperature is the same as described above.
The lactone ring-containing polymer, the N-substituted maleimide ring-containing polymer and the tetrahydropyran ring-containing polymer may be a mixture (blend) of two or more polymers, for example, an N-substituted maleimide ring containing Tg = 120 ° C. The form etc. which mix 40 mass% of polymers and 60 mass% of N substituted maleimide ring containing polymers of Tg = 90 degreeC can be mentioned. In such a case, the glass transition temperature of the entire mixture is preferably within the above-mentioned range. The method for measuring the glass transition temperature in the case of such a mixture is the same as described above.

The lactone ring-containing polymer, N-substituted maleimide ring-containing polymer, and tetrahydropyran ring-containing polymer may be thermoplastic or thermosetting, preferably thermoplastic. It is what has.
In addition to the lactone ring-containing polymer, N-substituted maleimide ring-containing polymer, and tetrahydropyran ring-containing polymer, examples of the binder resin in the present invention include (meth) acrylic resins and (meth) acrylurethane resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, melamine resin, urethane resin, styrene resin, alkyd resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, olefin resin, polyester Resins, (meth) acrylic silicone resins, alkylpolysiloxane resins, silicone resins, silicone alkyd resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins and other modified silicone resins, polyvinylidene fluoride, fluoro resins It may contain a fluorine-based resin such as fins vinyl ether polymer. Such a resin may be a thermoplastic resin, or a curable resin such as a thermosetting resin, a moisture curable resin, an ultraviolet curable resin, or an electron beam curable resin, but is preferably a thermoplastic resin. . In addition, organic binder resins such as synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, or natural rubber; silica sol, alkali silicate, silicon alkoxide and their ( Hydrolysis) Conventionally known binder resins such as condensates and inorganic binders such as phosphates can be mentioned. Among these, (meth) acrylic resins, (meth) acrylic urethane resins, and polyvinylidene fluoride can be formed by drying at a relatively low temperature and improving the durability of pigments. Fluorine resins such as fluoroolefin vinyl ether polymers, polycarbonate resins, polyarylate resins such as “ARTON” (manufactured by JSR), “O-PET” (manufactured by Kanebo) and “ZEONOR” (manufactured by Nippon Zeon) The olefin resin such as) may be blended or grafted. However, as described above, when the content of the lactone ring, N-substituted maleimide ring or tetrahydropyran ring-containing polymer is 100% by mass in terms of nonvolatile content, the resin composition of the present invention is 20% by mass or more and 99.9995% by mass. % Or less is preferable. As described above, the glass transition temperature of the blend or the entire grafted product is preferably 90 ° C. or higher and 200 ° C. or lower.

The resin composition of the present invention may contain a crosslinking agent. There are no particular limitations on the amount of the crosslinking agent used or the method of addition and dispersion. For example, when the binder resin is composed of a polyol having a plurality of hydroxyl groups in one molecule, the amount usually used for the polyol and addition And a dispersion method.
Examples of the crosslinking agent include a (block) polyisocyanate compound and an aminoplast resin when the binder resin is composed of a polyol.

The resin composition of the present invention may contain, for example, a solvent, an additive and the like in addition to the constituent elements such as the dye and the binder resin described above. As such a solvent, the thing similar to what was mentioned above can be used. In addition, as the additive, a conventionally known additive generally used in a resin composition for forming a film, a coating film, or the like can be used. For example, a leveling agent; inorganic fine particles such as colloidal silica and alumina sol; Anti-sagging agent, silane coupling agent, titanium white, carbon black, organic pigment, pigment intermediate and other pigments; pigment dispersant; viscosity modifier; UV stabilizer; metal deactivator; A filler, a plasticizer, a rust inhibitor, a fluorescent brightener, an organic and inorganic ultraviolet absorber, an inorganic heat absorber, an organic / inorganic flame retardant, and an antistatic agent.

The resin composition may further contain a dehydrating agent in order to improve the thermal stability of the dye in the resin composition containing the dye. As the dehydrating agent, there are various inorganic compounds or organic compounds, but from the viewpoint of coating film performance, it is preferable that it is volatilized at the time of coating film formation and does not remain in the coating film. It is preferable to use an organic dehydrating agent that easily volatilizes. Examples of such dehydrating agents include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate, ethyl silicate and the like. A hydrolysable ester compound is mentioned.
The content of the dehydrating agent is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. If the amount is less than 1 part by weight, the effect of the dehydrating agent may not be sufficiently exhibited. If the amount exceeds 20 parts by weight, the physical properties of the coating film may not be sufficiently improved. More preferably, it is 2-10 weight part, More preferably, it is 3-7 weight part.

As the resin composition of the present invention, a lactone ring, N-substituted maleimide ring or tetrahydropyran ring-containing polymer obtained by the above-described production method, and a dye are mixed, and if necessary, other binder resins, It can be obtained by mixing additives, solvents and the like.
As the usage form of the resin composition, for example, a coating film is formed, and the coating film is provided on a transparent substrate as a layer that absorbs at least one of visible light, near infrared light, and neon light. The form made into a body, the form made into the laminated body pinched | interposed between two transparent base materials, etc. can be mentioned. As the coating film, either crosslinked or uncrosslinked can be used, and in the case of forming a crosslinked coating film, for example, it is cured by crosslinking itself or by crosslinking by adding a crosslinking agent. It is preferable to form a coating film.
Examples of the transparent base include organic bases such as polycarbonate resins, acrylic resins, polyethylene resins, polyester resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, and cellulose resins; inorganic bases such as glass Materials and the like. Moreover, the transparent base material may be colored and various designs may be printed.

Examples of a method for forming a layer that absorbs at least one of visible light, near infrared light, and neon light include: (1) a resin composition of the present invention applied on a transparent substrate and then applied; A method of drying and / or cross-linking the product to form a layer that absorbs at least one of visible light, near infrared light, and neon light, (2) forming the resin composition of the present invention into a film, Examples include a method of forming a layer that absorbs at least one of visible light, near infrared light, and neon light by sticking to a transparent substrate. The method (1) is preferable because it is simple.

Examples of the method for applying the resin composition include immersion, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating, blade coating, bar coating, reverse coating, die coating, spray coating, and electrostatic coating. And the like. In these cases, the above-mentioned solvent can be appropriately mixed and applied to the resin composition. Moreover, what is necessary is just to set suitably according to the kind etc. of binder resin as a method of drying and / or crosslinking-hardening a resin composition, for example, the method of heating, the method of irradiating an ultraviolet-ray or an electron beam, etc. are mentioned.
What is necessary is just to set suitably as thickness of the said coating film by a use application etc., For example, it is preferable to make it the thickness after drying become 0.5-1000 micrometers. More preferably, it is 1-100 micrometers. More preferably, it is 3-50 micrometers, Most preferably, it is 5-20 micrometers.

The resin composition of the present invention is used for front filters used for preventing infrared remote control malfunction and improving color reproducibility in displays such as plasma displays, as well as for windows in buildings and houses, trains, automobiles, etc. It can also be used for vehicle windows, arcades, greenhouses, solar panel protection filters, sunglasses, general glasses, protective glasses, contact lenses, and the like. Furthermore, films and sheets for optical, agricultural, architectural, vehicle, image recording, etc., solar cells such as refrigeration / refrigeration showcases, dye-sensitized solar cells, infrared / visible luminescence ink, optical disks, etc. It can also be used as an information recording material, an eye strain prevention agent, a photothermal conversion material such as photosensitive paper, and an adhesive for laser transmission melting.

The resin composition of the present invention has the above-described configuration, can achieve both durability and flexibility of the pigment, and has improved stability of the pigment in the resin liquid. A layer that absorbs at least one of infrared rays or neon rays can be formed, and the layer can be used for various purposes.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Synthesis example of lactone ring-containing polymer>
(Synthesis Example 1)
In a 500 mL flask equipped with a stirrer, dropping port, thermometer, condenser and nitrogen gas, 30 g of methyl 2- (hydroxymethyl) acrylate (MHMA), 70 g of methyl methacrylate (MMA), 50 g of methyl isobutyl ketone (MIBK) Was charged. When refluxed while introducing nitrogen, 0.064 g of tertiary butyl peroxyisopropyl carbonate (TBPC) was added as an initial initiator, and at the same time, a solution comprising 0.064 g of TBPC and 70 g of MIBK as an initiator for dropping. The solution was polymerized under reflux while dropwise adding for 4 hours. Four hours after dropping the initiator, 30 g of MIBK was added, and further aging was performed for 4 hours. While adding 0.005 g of stearyl phosphate / distearyl phosphate mixture (“Phoslex A-18” manufactured by Sakai Chemical Co., Ltd.) to 1 g of the polymer component of the polymer solution obtained as described above, The cyclization condensation reaction was performed for 5 hours under reflux. Next, after attaching a distillation apparatus to the flask, 30 g of toluene was added as an azeotropic solvent, and nitrogen bubbling and oil bath temperature increase were started. The oil bath was heated to the reflux temperature while water and alcohol in the system were distilled out of the system. When the amount of distillate decreases, sampling is performed and the residual moisture content is measured by a Karl Fischer automatic moisture analyzer. After confirming that the moisture content in the system is 1000 ppm or less, the flask is cooled to room temperature. And diluted with methyl ethyl ketone so that the non-volatile content was 25%. When the obtained reaction solution was measured for dynamic TG, the weight loss rate was 0.69%. Moreover, the weight average molecular weight was 244000 and the glass transition temperature was 139 degreeC.

(Measurement of weight average molecular weight and number average molecular weight)
The molecular weight in terms of polystyrene was determined by GPC (manufactured by Tosoh Corporation, HLC8120, column is TSK-GEL GMHXL-L).
(Measurement of dealcoholization reaction rate)
The dealcoholization reaction rate is based on the mass loss that occurs when all hydroxyl groups are dealcoholated as methanol from the polymer composition obtained by polymerization, and the weight loss starts from 150 ° C. before the mass loss starts in dynamic TG measurement described later. It calculated | required from the mass reduction by the dealcoholization reaction to 300 degreeC before decomposition | disassembly of coalescence started.
That is, in the dynamic TG measurement of a polymer having a lactone ring structure, the mass reduction rate between 150 ° C. and 300 ° C. is measured, and the obtained actual mass reduction rate is defined as (X). On the other hand, from the composition of the polymer, all the hydroxyl groups contained in the polymer composition are involved in the formation of the lactone ring, so that it becomes an alcohol and is dealcoholized. The mass reduction rate calculated on the assumption that a% dealcoholization reaction has occurred is defined as (Y). The theoretical mass reduction rate (Y) is more specifically the molar ratio of the raw material monomers having a structure (hydroxyl group) involved in the dealcoholization reaction in the polymer, that is, the raw material unit in the polymer composition. It can be calculated from the content of the monomer. These values (X, Y) are calculated as a dealcoholization formula;
1- (actual mass reduction rate (X) / theoretical mass reduction rate (Y))
Substituting into, the value is obtained and expressed in% to obtain the dealcoholization reaction rate. And the content (mass ratio) in the said polymer composition of the raw material monomer which has the structure (aquatic group) which participates in lactone cyclization as what the predetermined lactone cyclization was performed only by this dealcoholization reaction rate The ratio of the lactone ring structure in the polymer can be calculated by multiplying the reaction rate by the dealcoholization reaction rate.

For example, the proportion of the lactone ring structure in the polymer obtained in Example 1 described later is calculated. When the theoretical mass reduction rate (Y) of this polymer was determined, the molecular weight of methanol was 32, the molecular weight of methyl 2- (hydroxymethyl) acrylate was 116, and methyl 2- (hydroxymethyl) acrylate. Since the content (mass ratio) in the polymer is 30.0% by mass in terms of composition, (32/116) × 30.0≈8.28% by mass. On the other hand, the actual mass reduction rate (X) by dynamic TG measurement was 0.69% by mass. When these values are applied to the above-described dealcoholization calculation formula, 1− (0.69 / 8.28) = 0.92, and the dealcoholization reaction rate is 92.0%. And in the polymer, the content (30.0% by mass) of 2- (hydroxymethyl) methyl acrylate in the polymer, assuming that the predetermined lactone cyclization was performed for the dealcoholization reaction rate, When multiplied by the dealcoholization reaction rate (92.0% = 0.92), the proportion of the lactone ring structure in the polymer is 27.6 (30.0 × 0.92) mass%.

[Dynamic TG measurement]
The obtained lactone ring-containing polymer solution is put into excess n-hexane to perform reprecipitation, and the taken out precipitate is vacuum-dried (1 mmHg (133 Pa), 80 ° C., 3 hours or more), whereby volatile components, etc. The white solid resin thus obtained was analyzed by the following method (dynamic TG method).
Measuring device: Thermo Plus2 TG-8120 DynamicTG (manufactured by Rigaku Corporation)
(Measurement condition)
Sample amount: 5-10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200ml / min
Method: Step-like isothermal control method (controlled at a weight reduction rate value of 0.005% / sec or less between 60 ° C. and 500 ° C.)

[Measurement of glass transition temperature (Tg)]
The obtained lactone ring-containing polymer solution is put into excess n-hexane to perform reprecipitation, and the taken out precipitate is vacuum-dried (1 mmHg (133 Pa), 80 ° C., 3 hours or more), whereby volatile components, etc. The obtained white solid resin was pulverized with an agate mortar, and the glass transition temperature was measured by the following method using a sample having a uniform particle size with a 50 mesh wire mesh.
Measuring device: DSC220 (manufactured by Seiko Electronics Industry)
(Measurement condition)
Sample amount: about 5mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 30 ml / min
Method: The maximum value of DDSC (mW / min) was taken as the glass transition temperature.

(Synthesis Examples 2-6 and 9)
A polymer solution was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of monomers charged in the flask were changed as shown in Table 1.

(Synthesis Example 7)
In a 500 mL flask equipped with a stirrer, dropping port, thermometer, condenser and nitrogen gas, 60 g of methyl methacrylate (MMA), 40 g of dicyclopentanyl methacrylate (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.), methyl isobutyl Ketone (MIBK) 50g was charged. When refluxed while introducing nitrogen, 0.064 g of tertiary butyl peroxyisopropyl carbonate (TBPC) was added as an initial initiator, and at the same time, a solution comprising 0.064 g of TBPC and 70 g of MIBK as an initiator for dropping. The solution was polymerized under reflux while dropwise adding for 4 hours. Four hours after dropping the initiator, 30 g of MIBK was added, and further aging was performed for 4 hours. Then, it diluted with methyl ethyl ketone so that a non volatile matter might be 25%. The weight average molecular weight of the obtained polymer was 302000, and the glass transition temperature was 125 ° C.

(Synthesis Example 8)
A polymer solution was obtained in the same manner as in Synthesis Example 7 except that the types and amounts of monomers charged in the flask and the initiator amount were changed as shown in Table 1.

Table 1 will be described below.
MHMA; methyl 2- (hydroxymethyl) acrylate MMA; methyl methacrylate CHMA; cyclohexyl methacrylate TBMA; tert-butyl methacrylate FM-108; perfluorooctylethyl methacrylate (trade name: Light Ester FM108, manufactured by Kyoeisha Chemical Co., Ltd.)
MAA; methacrylic acid FA-513M; dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.)
MIBK; Methyl isobutyl ketone TBPC; Tertiary butyl peroxyisopropyl carbonate MEK; Methyl ethyl ketone

<Synthesis Example of Tetrahydropyran Ring-Containing Polymer Using Monomer (Ether Dimer) Represented by General Formula (6)>
(Synthesis Example 10)
In a 500 mL flask equipped with a stirrer, a dripping port, a thermometer, a condenser tube and nitrogen gas, 150 g of propylene glycol monomethyl ether acetate (PGMAC) was charged, and the temperature was raised to 100 ° C. while passing nitrogen through the flask. On the other hand, 15 g of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD), 73 g of methyl methacrylate (MMA), 10 g of tert-butyl methacrylate (TBMA), methacrylic acid (MAA) ) 2 g and 2 g of tertiary butyl peroxy-2-ethylhexanoate (PBO) as an initiator were added and the mixture was added dropwise over 2 hours. After 4 hours from the start of dropping, 36 g of PGMAC was added, and further aging was performed for 2 hours. Thereafter, it was diluted with methyl ethyl ketone so that the nonvolatile content was 25%. The weight average molecular weight was 35000, and the glass transition temperature was 115 ° C.

(Synthesis Example 11)
A tetrahydropyran ring-containing polymer was obtained in the same manner as in Synthesis Example 10 except that the type and amount of the monomer charged in the dropping tank were changed as shown in Table 2.

<Synthesis Example of N-Substituted Maleimide-Containing Polymer>
(Synthesis Example 12)
To a 500 mL flask equipped with a stirrer, a dripping port, a thermometer, a condenser tube and nitrogen gas, 40 g of toluene and 25 g of N-cyclohexylmaleimide were charged. On the other hand, 75 g of methyl methacrylate (MMA) is added to the dropping tank, and 2,2-bis (4,4-ditertiary butyl peroxycyclohexyl) propane (BDBCP, manufactured by Kayaku Akzo "Parkadox 12-XL25" as an initiator. ]) 1.5 g was charged and 60% of this mixture was charged to the flask. While passing nitrogen through the flask, the temperature was raised to 100 ° C., and the remaining mixture charged in the dropping tank was dropped over 30 minutes. Three hours after the start of dropping, 100 g of toluene was added, and the temperature was raised to reflux. After aging, the mixture was further aged for 4 hours, and diluted with methyl ethyl ketone so that the nonvolatile content was 25%. The weight average molecular weight was 322000, and the glass transition temperature was 130 ° C.

(Synthesis Examples 13 to 16)
An N-substituted maleimide-containing polymer was obtained in the same manner as in Synthesis Example 12 except that the type and amount of the monomer charged in the dropping tank were changed as shown in Table 2.

(Synthesis Example 17)
To a 500 mL flask equipped with a stirrer, a dripping port, a thermometer, a condenser tube and nitrogen gas, 40 g of toluene and 10 g of N-cyclohexylmaleimide were charged. On the other hand, 60 g of methyl methacrylate (MMA), 10 g of normal butyl methacrylate (BMA) in the dropping tank, 2,2-bis (4,4-ditertiary butyl peroxycyclohexyl) propanone (BDBCP, Kayaku Akzo Co., Ltd.) as an initiator 1.5 g (manufactured “Perkadox 12-XL25”) was charged, and 60% of this mixture was charged into the flask. While passing nitrogen through the flask, the temperature was raised to 100 ° C., and the remaining mixture charged in the dropping tank was dropped over 30 minutes. Three hours after the start of dropping, 100 g of toluene was added, and the temperature was raised to reflux. After aging, the mixture was further aged for 4 hours, and diluted with methyl ethyl ketone so that the nonvolatile content was 25%. The weight average molecular weight was 304000, and the glass transition temperature was 92 ° C.

(Synthesis Example 18)
40 g of toluene was charged into a 500 mL flask equipped with a stirrer, a dripping port, a thermometer, a condenser tube and nitrogen gas. On the other hand, 100 g of methyl methacrylate (MMA) is added to the dropping tank, and 2,2-bis (4,4-ditertiary butyl peroxycyclohexyl) propane (BDBCP, “Perkadox 12-XL25” manufactured by Kayaku Akzo) as an initiator. 1.5g was charged and 20% of this mixture was charged to the flask. While passing nitrogen through the flask, the temperature was raised to the reflux temperature (about 110 ° C.), and the remaining mixture charged in the dropping tank was dropped over 60 minutes. Three hours after the start of dropping, 100 g of toluene was added. After completion of the dropping, the mixture was further aged for 4 hours and then diluted with methyl ethyl ketone so that the nonvolatile content was 25%. The weight average molecular weight was 221000, and the glass transition temperature was 105 ° C.

Table 2 will be described below.
MD; dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate MMA; methyl methacrylate BMA; normal butyl methacrylate ST; styrene CHMA; cyclohexyl TBMA; tert-butyl methacrylate MAA; methacrylic acid PBO; tert-butyl-peroxy-2-ethylhexanoate BDBCP; 2,2-bis (4,4-ditertiary butyl peroxycyclohexyl) propane (“PARCADOX 12-XL25” manufactured by Kayaku Akzo)
PGMAC; propylene glycol monomethyl ether acetate MEK; methyl ethyl ketone

(Example 1)
A resin composition was prepared by blending 40 g of the acrylic polymer of Synthesis Example 1 as a binder resin, 0.1 g of a diimonium salt dye (manufactured by Nippon Kayaku Co., Ltd., IRG-022) and 10 g of methyl ethyl ketone. This resin composition was allowed to stand for 30 days in an atmosphere of 40 ° C., and the stability of the dye was evaluated in the resin solution. Also, the resin composition immediately after blending the pigment was coated on one side of a 188 micron thick PET film (“A-4100” manufactured by Toyobo Co., Ltd.) whose both surfaces were subjected to easy adhesion treatment so that the dry film thickness was 10 μm. And dried at 120 ° C. for 3 minutes. The obtained coating film was subjected to a heat and humidity resistance test, a heat resistance test, and a flexibility test. The results are shown in Table 3.

(Examples 2-18 and Comparative Examples 1-2)
Except as shown in Table 3 and Table 4, it was blended with the dye in the same manner as in Example 1, and the stability of the dye in the resin solution, the wet heat resistance test of the coated film, the heat resistance test, the flexibility test Went. The results are shown in Tables 3 and 4.

1) Paint stability of resin composition As shown in Tables 3 and 4, the resin composition containing the pigment and each binder is allowed to stand at 40 ° C for 30 days. The film was coated on one side of a 188 micron thick PET film (“A-4100” manufactured by Toyobo Co., Ltd.) so as to have a dry film thickness of 10 μm and dried at 120 ° C. for 3 minutes. The transmittance of the obtained coating film was measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100) using an integrating sphere to measure the transmittance for incident light from the dye-containing coating layer, and before and after the stability test. The difference of the transmittance | permeability in the maximum absorption wavelength of this pigment | dye was calculated | required, and the stability of the pigment | dye in a resin composition was evaluated on the following reference | standard.
[Evaluation criteria for dye stability]
○: Change in transmittance at the maximum absorption wavelength of the dye before and after the test; less than 1% Δ: Change in transmittance at the maximum absorption wavelength of the dye before and after the test; 1% or more and less than 3% ×; Change in transmittance at maximum absorption wavelength; 3% or more

2) Heat-and-moisture resistance The coated film was allowed to stand for 250 hours and 500 hours in a high-temperature and high-humidity atmosphere at 80 ° C. and a relative humidity of 95%. The transmittance at the maximum absorption wavelength of the dye used before and after standing was measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100) using an integrating sphere, and the difference in transmittance before and after standing was determined. The stability of the pigment in the coating was evaluated. The smaller the difference in transmittance before and after the test, the better the stability of the dye. Moreover, in order to evaluate the base-material adhesiveness of the coating film after leaving for 250 hours and 500 hours, the cross-cut tape peeling test based on JISK56008.5 is performed, and the coating-film state after a peeling test is based on the following reference | standard. It was evaluated with.
[Evaluation criteria for dye stability]
○ (good): change in transmittance at the maximum absorption wavelength of the dye before and after the test; less than 1% Δ (slightly good); change in transmittance at the maximum absorption wavelength of the dye before and after the test; × (Inferior): Change in transmittance at maximum absorption wavelength of the dye before and after the test; 3% or more [Evaluation criteria for substrate adhesion]
○: No abnormality, △: Slight peeling, ×: Peeling

3) The coated film is allowed to stand for 250 hours and 500 hours in an atmosphere having a heat resistance of 100 ° C., and the transmittance at the maximum absorption wavelength of the dye used before and after being left is measured with a spectrophotometer in the same manner as described above. The stability of the pigment in the coating film was evaluated according to the following criteria. The smaller the difference in transmittance before and after the test, the better the stability of the dye.
[Evaluation criteria for dye stability]
○ (good): change in transmittance at the maximum absorption wavelength of the dye before and after the test; less than 1% Δ (slightly good); change in transmittance at the maximum absorption wavelength of the dye before and after the test; × (Inferior): Change in transmittance at the maximum absorption wavelength of the dye before and after the test; 3% or more

4) A bendability test was conducted on the bendable film based on JIS K5400 8.1, and evaluated by the diameter of the mandrel in which abnormalities such as cracks and peeling occurred in the bend of the paint film. did. The smaller the diameter of the mandrel, the better the flexibility of the coating film.
[Evaluation criteria for coating flexibility]
○ (good); the diameter of the mandrel is 6 mm or less Δ (somewhat good); the diameter of the mandrel is 8 mm or more and 10 mm or less × (inferior);

Reference example 1
A film was prepared as follows using a resin composition containing a binder resin and a pigment.
[Preparation of low refractive index coating agent (S-1)]
1) Synthesis of polymerizable polysiloxane (M-1) In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 g of tetramethoxysilane, 23.6 g of γ-methacryloxypropyltrimethoxysilane, 19.0 g of water, 30.0 g of methanol, and 5.0 g of Amberlyst 15 (trade name, cation exchange resin manufactured by Organo) were added and stirred at 65 ° C. for 2 hours for reaction. After the reaction mixture is cooled to room temperature, a distillation column, a cooling tube connected to the distillation column and an outlet are provided instead of the cooling tube, and the temperature inside the flask is raised to about 80 ° C. over 2 hours under normal pressure. It was kept at the same temperature at which it did not flow out. Further, the reaction was further proceeded by maintaining at a temperature of 90 ° C. under a pressure of 2.67 × 10 kPa until methanol no longer flows out. After cooling to room temperature again, Amberlyst 15 was filtered off to obtain polymerizable polysiloxane (M-1) having a number average molecular weight of 1800.

2) Synthesis of organic polymer (P-1) 260 g of n-butyl acetate as an organic solvent was placed in a 1 liter flask equipped with a stirrer, a dropping port, a thermometer, a condenser tube and an N ₂ gas inlet, and N ₂ The temperature inside the flask was heated to 110 ° C. while introducing gas and stirring. Then, 12 g of polymerizable polysiloxane (M-1), 19 g of tert-butyl methacrylate, 94 g of butyl acrylate, 67 g of 2-hydroxyethyl methacrylate, 48 g of perfluorooctylethyl methacrylate (Light Ester FM-108, manufactured by Kyoeisha Chemical Co., Ltd.), 2 , 2'-azobis- (2-methylbutyronitrile) 2.5 g mixed solution was added dropwise from the dropping port over 3 hours. After the dropwise addition, stirring was continued at the same temperature for 1 hour, and then 0.1 g of tert-butylperoxy-2-ethylhexanoate was added twice every 30 minutes, and the mixture was further heated for 2 hours for copolymerization. A solution in which an organic polymer (P-1) having an average molecular weight of 12000 and a weight average molecular weight of 27000 was dissolved in n-butyl acetate was obtained. The solid content of the obtained solution was 48.2%.

3) Synthetic stirrer of low refractive index coating agent (S-1), two dropping ports (dropping port 1 and dropping port 2), a 500 ml four-necked flask equipped with a thermometer, 200 g of n-butyl acetate, 50 g of methanol was added and the internal temperature was adjusted to 40 ° C. Next, while stirring the inside of the flask, a mixed solution (raw material solution A) of 10 g of an n-butyl acetate solution of organic polymer (P-1), 30 g of tetramethoxysilane and 5 g of n-butyl acetate was added from a dropping port 1 with 25% ammonia. A mixed solution (raw material solution B) of 5 g of water, 10 g of deionized water, and 15 g of methanol was dropped from the dropping port 2 over 2 hours. After dropping, a distillation column, a cooling pipe connected to this, and an outlet are provided instead of the cooling pipe, and the temperature inside the flask is raised to 100 ° C. under a pressure of 40 kPa, and ammonia, methanol, and n-butyl acetate are solidified. The solvent was distilled off until the content became 30% to obtain a low refractive index coating agent (S-1) having a ratio of inorganic fine particles to organic polymer of 70/30. The average particle size of the inorganic fine particles in the low refractive index coating agent was 23.9 nm. The analysis was performed by the following method.

<Ratio of inorganic fine particles and organic polymer in low refractive index coating agent>
Elemental analysis was performed on the low refractive index coating agent dried at 130 ° C. for 24 hours under a pressure of 1.33 × 10 kPa, and the ash content was determined as the content of inorganic fine particles in the low refractive index coating agent.
<Average particle size>
Using a solution obtained by diluting 1 g of low refractive index coating agent (S-1) with 99 g of n-butyl acetate, the particles were photographed with a transmission electron microscope, the diameters of 100 arbitrary particles were read, and the average was averaged. The particle diameter was obtained.

[Production of composite film having anti-reflection and near-infrared cutting ability]
1) Preparation of hard coating agent (A) 8 g of dipentaerythritol hexaacrylate (light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) and 2 g of pentaerythritol triacrylate (light acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed. A solution prepared by dissolving 0.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) in 2 g of methyl ethyl ketone was added to a solution dissolved in 40 g of methyl ethyl ketone to prepare a hard coat layer coating solution.

2) Preparation of low refractive index coating agent (B) 9 g of low refractive index coating agent (S-1), Desmodur N3200 (trade name, Isocyanate hardener made by Sumika Bayer Urethane Co., Ltd.), 0.3 g of dilauric acid 0.003 g of n-butyltin and 110 g of methyl isobutyl ketone were mixed to prepare a low refractive index layer coating solution.
3) Preparation of near-infrared cut coating agent (C) Resin composition containing 40 parts of the acrylic polymer of Synthesis Example 2, 0.1 g of diimonium salt dye (manufactured by Nippon Kayaku Co., Ltd., IRG-022) and 10 g of methyl ethyl ketone. Was prepared.

4) Production of composite film having antireflection ability and near-infrared cutting ability Using a bar coater with the above hard coat agent (A) on one side of a 188 μm thick polyethylene terephthalate film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) After coating at 100 ° C. for 15 minutes, the coating layer was cured by irradiating 200 mJ / cm ² of ultraviolet light with a high pressure mercury lamp to form a hard coating layer having a thickness of 5 μm. Next, on the hard coat layer, the low refractive index coating agent (B) is applied using a bar coater and cured at 100 ° C. for 1 hour to form a low refractive index layer having a thickness of 0.1 μm. did. Next, the near-infrared cut coating agent (C) was applied to the opposite side of the low refractive index layer so that the dry film thickness was 10 μm, and dried at 120 ° C. for 5 minutes to form a near-infrared cut layer. Thus, the composite film which has a low refractive index layer, a hard-coat layer, a polyethylene terephthalate film layer, and a near-infrared cut layer in this order, and has antireflection ability and near-infrared cut ability was produced. The reflectance of the obtained composite film was 0.45% at a wavelength of 550 nm. In addition, when the obtained composite film was subjected to a moisture and heat resistance test, a heat resistance test, and a flexibility test under the same conditions as described above, as shown in Table 5, it was excellent in bendability and was resistant to moisture and heat after the test. It was an excellent film.

<Measurement of reflectance>
For the film prepared as described above (initial value) and the film after 500 hours of moisture and heat resistance test, the surface opposite to the antireflection film side of the film is roughened with steel wool, and further black ink is applied to prevent reflection. The specular reflection spectrum of the film-side surface at an incident angle of 5 ° is measured using an ultraviolet-visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), and the wavelength at which the reflectance is a minimum value and the minimum value of the reflectance. Asked. The results are shown in Table 5.

Claims (4)

A resin composition used for forming a layer that absorbs at least one of visible light, near infrared light, and neon light,
The resin composition comprises a dye having a maximum absorption wavelength at 380 to 1200 nm and a polymer containing a lactone ring, an N-substituted maleimide ring or a tetrahydropyran ring. The lactone ring-containing polymer has the following general formula (1);

(Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may have oxygen). The resin composition according to claim 1, which is a polymer having a structural unit represented. The N-substituted maleimide ring-containing polymer has the following general formula (4):

(Wherein R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group. R ⁹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group. The resin composition according to claim 1, which is a polymer having a structural unit represented by: The tetrahydropyran ring-containing polymer has the following general formula (5):

(Wherein R ¹⁰ and R ¹¹ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, an alicyclic hydrocarbon group or a substituted hydrocarbon group). The resin composition according to claim 1, which is a polymer having