JPH10152598A - Near-infrared absorption resin composition and material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that can improve the compatibility to resin as well as resistance against humidity, can manifest excellent transparency in the visible range and near infrared absorption and is useful as an optical filter. SOLUTION: This composition contains (A) a resin prepared by polymerizing a monomer bearing an unsaturated double bond, (B) a compound of formula I R is a 1-18C alkyl, aryl, aralkyl, alkenyl; OR is a 4-100C polyoxyalkyl, a (meth)acryloyl(poly)oxyalkyl [for example, may be a group of formula II (X is H, methyl; Y is a 2-4C oxyalkylene; m is a number-average value of 1-20]; n is 1, 2} and (C) copper hydroxide. In a preferred embodiment, the amounts of the components B and C are 0.5-30 pts.wt. and 0.1-20 pts.wt. per 100 pts.wt. of the component A, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is transparent in the visible region,
The present invention also relates to a resin composition having a near-infrared wavelength light absorption performance.

[0002]

2. Description of the Related Art Resin compositions that absorb light having a wavelength in the near-infrared region have been used as optical filters or as heat ray absorbing materials, and various compositions have already been proposed.

For example, Japanese Patent Publication No. Sho 62-5190 and Japanese Patent Publication No. Sho 63-31512 disclose methacrylic resin 10 selected from polymethyl methacrylate or a methacrylic polymer containing 50% by weight or more of methyl methacrylate units.
0.01 to 5 parts by weight of an organic compound containing a divalent copper ion in terms of the weight of the copper ion with respect to 0 parts by weight, and a solar radiation absorbing ability containing a phosphorus compound having a specific structure. Excellent methacrylic resin materials have been proposed.
JP-A-6-118228 discloses a copolymer obtained by copolymerizing a monomer containing a phosphate group-containing monomer having a specific structure and a monomer copolymerizable therewith, and a copper salt. An optical filter characterized by containing a metal salt containing as a main component has been proposed.

[0004]

However, the materials disclosed in JP-B-62-5190 and JP-B-63-31512 have a large absorption in the near-infrared region, but have a large hygroscopic property, and can be used in a high-humidity atmosphere. Easily devitrified when used. Further, the material described in JP-A-6-118228 has a sufficient near-infrared absorption capability, but has a large hygroscopicity and easily devitrifies when used in a high-humidity atmosphere. It is not industrially preferable, for example, it has a step of extracting an acid component. In view of such circumstances, the present inventors have conducted intensive studies to improve the hygroscopicity of the near-infrared absorbing resin composition, and as a result, conventionally, copper benzoate, copper acetate, as a copper compound to improve compatibility with the resin, Although copper salts of organic carboxylic acids such as copper naphthenate were used, it was found that by using copper hydroxide, moisture resistance can be improved without changing the compatibility with the resin. Invented the invention.

[0005]

That is, the present invention is a near-infrared absorbing resin composition containing the following components (a) to (c). (A) Resin obtained by polymerizing a monomer having an unsaturated double bond (b) General formula

(OH) _n -P (O)-(OR) _3-n (wherein R is an alkyl group having 1 to 18 carbon atoms, aryl group, aralkyl group, alkenyl group, or RO is A phosphorus atom-containing compound represented by 4 to 100 polyoxyalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloylpolyoxyalkyl group, and n represents 1 or 2) (c) copper hydroxide

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, a resin obtained by polymerizing a monomer having an unsaturated double bond as the component (a) refers to a monofunctional or polyfunctional monofunctional compound having at least one radically polymerizable unsaturated double bond in a molecule. The resin obtained by polymerizing the monomer is not particularly limited as long as it is a resin transparent in the visible light region.

As monofunctional monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate,
(Meth) acrylic esters having a linear or branched alkyl group such as n-lauryl (meth) acrylate and n-stearyl (meth) acrylate; bornyl (meth) acrylate, fentyl (meth) acrylate,
1-menthyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.
1.0 ^2,6 ] dec-8-yl = (meth) acrylate;
(Meth) acrylates having an alicyclic hydrocarbon group such as dicyclopentenyl (meth) acrylate; alkenyl groups such as allyl (meth) acrylate, benzyl (meth) acrylate, and naphthyl (meth) acrylate; (Meth) acrylic esters having an aryl group; styrene monomers such as styrene, α-methylstyrene, vinyltoluenechlorostyrene and bromostyrene; unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and itaconic acid Acid anhydrides such as acid, maleic anhydride and itaconic anhydride; hydroxyls such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and monoglycerol (meth) acrylate Group containing Monomers; nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate; epoxy group-containing monomers such as allyl glycidyl ether and glycidyl (meth) acrylate; polyethylene Alkylene oxide group-containing monomers such as glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol monoallyl ether; other single monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, and ethylene Examples include a body, but are not particularly limited thereto.

Examples of the polyfunctional monomer include alkyl diol di (meth) acrylates such as ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate.
Acrylates: tetraethylene glycol di (meth)
Alkylene glycol di (meth) acrylates such as acrylate and tetrapropylene glycol diacrylate; aromatic polyfunctional compounds such as divinylbenzene and diallyl phthalate; pentaerythritol tetra (meth) acrylate and trimethylolpropane tri (meth) acrylate Examples of such polyhydric alcohol (meth) acrylates include, but are not particularly limited to, these.

The above (meth) acrylate indicates that it is acrylate or methacrylate.
Among the above monomers, (meth) acrylates are preferably used from the viewpoints of availability and transparency of the obtained resin. Note that two or more of the above monofunctional monomers and / or polyfunctional monomers can be used in combination. The resin of the component (a) can be easily obtained by a known polymerization method, for example, bulk polymerization, suspension polymerization, emulsion polymerization and the like. Further, this resin may contain various additives and the like as long as the performance is not deteriorated.

The phosphorus atom-containing compound as the component (b) in the present invention is represented by the following general formula (3), and the RO in the general formula (3) is represented by the following general formula (4).

Embedded image wherein CH 2 ＣC (X) COO (Y) _m − (wherein X is a hydrogen atom or a methyl group, and Y is a group having 2 to 2 carbon atoms.
Oxyalkylene group, m represents a number average of 1 to 20), and in the case of a phosphorus atom-containing compound which is a (meth) acryloyloxyalkyl group or a (meth) acryloylpolyoxyalkyl group, A composition comprising a resin obtained by copolymerizing an atom-containing compound with a monomer having an unsaturated double bond constituting the resin of component (a) is included as a near-infrared absorbing resin composition, and is copolymerized. It is preferably used because the resulting resin increases the strength.

Examples of the phosphorus atom-containing compound include monoethyl phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, monohexyl phosphate, dihexyl phosphate, monoheptyl phosphate, diheptyl phosphate, and monooctyl phosphate. Alkyl phosphate with diatyl phosphate, dioctyl phosphate, monolauryl phosphate, dilauryl phosphate, monostearyl phosphate, distearyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, and naoto; mono Aryl phosphates such as phenyl phosphate and diphenyl phosphate; mono (nonylphenyl) phosphate and bis (nonylphenyl) phosphate Aralkyl phosphates such as phosphates; alkenyl phosphates such as monoallyl phosphate and diallyl phosphate; polyoxyalkyl phosphates such as polyethylene glycol phosphate; (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxy) (Meth) acryloyloxyalkyl phosphates such as ethyl] phosphate, (meth) acryloyloxypropyl phosphate, bis [(meth) acryloyloxypropyl] phosphate; (meth) acryloylpolyoxyethyl phosphate, (meth) acryloyl (Meth) acryloyl polyoxyalkyl phosphates such as polyoxypropyl phosphate. In addition, the said phosphorus atom containing compound can be used together 2 or more types.

The amount of the phosphorus atom-containing compound to be used is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the component (a). If the amount of the phosphorus atom-containing compound used is 0.1 parts by weight or less, good near-infrared absorbing ability cannot be obtained. On the other hand, if the amount is more than 50 parts by weight, the strength of the obtained copolymer decreases, which is not preferable.

The amount of copper hydroxide used as component (c) of the present invention is 0.01 to 30 parts by weight per 100 parts by weight of component (a).
Parts by weight, more preferably 0.1 to 20 parts by weight. If the amount of copper hydroxide used is 0.01 parts by weight or less, good near-infrared absorbing ability cannot be obtained. If the amount is more than 30 parts by weight, the transparency of the obtained resin in visible light is impaired, which is not preferable. This amount corresponds to approximately 0.05 to 10 mol of the phosphorus atom-containing monomer per 1 mol of copper hydroxide.

The resin composition of the present invention is a composition in which the above components (a), (b) and (c) are uniformly mixed. As the method, copper hydroxide is added to a mixture of an unsaturated monomer as the component (a) and a phosphorus atom-containing compound as the component (b), or a syrup containing a polymer or copolymer thereof. There is a method of uniformly dissolving and bulk-polymerizing, for example, polymerizing and curing in a cell or a mold and shaping into a predetermined shape. The polymerization at this time is carried out in the presence of a known radical polymerization initiator, or a method comprising a radical polymerization initiator and an accelerator, a so-called redox initiator, a method of irradiating ultraviolet rays or radiation, or the like. Can be performed by a known method.

Further, the resin of the powdery component (a) obtained by a known polymerization method, for example, bulk polymerization, suspension polymerization, emulsion polymerization, etc. is added to the phosphorus atom compound of the component (b) and the component (b). A method of uniformly mixing the copper hydroxide of c) by a well-known melt-kneading method, or an unsaturated monomer constituting the resin of the component (a) and (meth) acryloyloxyethyl phosphate of the component (b), etc. To the copolymer with
A method of uniformly blending the component (c) by a well-known melt-kneading method may also be used.

The resin composition of the present invention is formed into a desired shape by injection molding or extrusion molding, or is laminated on the surface of ordinary acrylic resin by coextrusion. It is formed into a desired shape according to. For example, it is used in the shape of a plate, a lens, a film, or the like. In this case, the thickness is approximately 0.
It is about 001 to 30 mm, and the size is 1 mm square to several 1
000 mm square.

The near-infrared absorbing material in this case has an average light transmittance of 50% or more from 400 nm to 650 nm and 800 n.
The average light transmittance from m to 1000 nm is desirably 30% or less, and the near infrared absorbing material obtained from the resin composition of the present invention satisfies this. 450 nm to 650
If the average light transmittance in nm is 50% or less, it cannot be seen through when used as an optical filter material or a heat ray absorbing material, which is not preferable. Also, from 800 nm to 100
If the average light transmittance at 0 nm is 30% or more, it will not function sufficiently as an optical filter material or a heat ray absorbing material.

The near-infrared absorbing resin composition of the present invention may optionally contain a light diffusing agent, a coloring agent, a reinforcing agent, a filler, a release agent,
It is also possible to add stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants and the like.

[0019]

The near-infrared absorbing resin composition of the present invention has excellent moisture resistance, is transparent in the visible region, and has the ability to absorb light in the near-infrared region. It can be suitably used as a filter or a heat ray absorbing glazing material.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The evaluation was performed by the following method. (1) Flexural strength: The flexural strength was measured according to JIS K6718. (2) Moisture resistance: A plate-like sample of a near-infrared absorbing material was immersed in boiling water for 1 hour and visually observed. (3) Near infrared absorption ability: 400 to 10 of the obtained sample
The spectral transmittance in the range of 00 nm was measured using a spectrophotometer U3410 manufactured by Hitachi, Ltd.

Example 1 The following chemical formula was added to 100 parts by weight of methyl methacrylate.
4 parts by weight of the phosphorus atom-containing compound represented by Chemical Formula 5 and 10 parts by weight of the phosphorus atom-containing compound represented by Chemical Formula 6 were added. 2 parts by weight of copper hydroxide and t-
0.5 parts by weight of butyl peroxy-2-ethylhexanoate was dissolved. This solution was poured into a polymerization cell consisting of a polyvinyl chloride gasket and two glass plates,
2 hours at 100 ° C for 2 hours at 100 ° C
Thus, a plate-like near-infrared absorbing material of m was obtained. Tables 1 and 2 show the evaluation results.
It was shown to.

[0022]

Embedded image CH ₂ CC (CH ₃ ) COOCH ₂ CH ₂ OP (O) (OH) ₂

[0023]

Embedded image [CH ₂ CC (CH ₃ ) COOCH ₂ CH ₂ O] ₂ -P (O) -OH

Example 2 In Example 1, the compound containing a phosphorus atom was represented by a chemical formula
Instead of the compounds represented by Chemical Formulas 5 and 6, the following chemical formula
A plate-like near-infrared absorbing material having a thickness of 3 mm was obtained in the same manner as in Example 1 except that 10 parts by weight of the compound represented by Chemical formula 7 was used. The evaluation results are shown in Tables 1 and 2.

[0025]

Embedded image CH ₂ CC (CH ₃ ) COO- [CH ₂ CH (CH ₃ ) O] _5.5 -P (O) (OH) ₂

Example 3 In Example 1, the compound containing a phosphorus atom was represented by a chemical formula
Instead of the compounds represented by Chemical Formulas 5 and 6, the following chemical formula
A plate-like near-infrared absorbing material having a thickness of 3 mm was obtained in the same manner as in Example 1, except that 4 parts by weight of the compound represented by Chemical Formula 8 and 10 parts by weight of the compound represented by Chemical Formula 9 were used. The evaluation results are shown in Tables 1 and 2.

[0027]

Embedded image CH ₂ CC (CH ₃ ) COO—CH ₂ CH (CH ₃ ) O—P (O) (OH) ₂

[0028]

Embedded image [CH ₂ CC (CH ₃ ) COO—CH ₂ CH (CH ₃ ) O] ₂ -P (O) OH

Comparative Example 1 The above chemical formula was added to 100 parts by weight of methyl methacrylate.
4 parts by weight of the compound represented by Chemical Formula 5 and 10 parts by weight of the compound represented by Chemical Formula 6 were added. 5 parts by weight of copper benzoate as a copper atom-containing compound and t-
0.5 parts by weight of butyl peroxy-2-ethylhexanoate was dissolved. This solution was poured into a polymerization cell consisting of a polyvinyl chloride gasket and two glass plates,
2 hours at 100 ° C for 2 hours at 100 ° C
Thus, a plate-like near-infrared absorbing material of m was obtained. Tables 1 and 2 show the evaluation results.
It was shown to.

[0030]

[Table 1]

[0031]

[Table 2]

Claims (3)

[Claims] A near infrared absorbing resin composition comprising the following components (a) to (c): (A) A resin obtained by polymerizing a monomer having an unsaturated double bond. (B) General formula (1) (OH) _n -P (O)-(OR) _3-n (wherein R represents an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or an alkenyl group, or RO represents a polyoxyalkyl group having 4 to 100 carbon atoms, a (meth) acryloyloxyalkyl group, or a (meth) acryloylpolyoxyalkyl. Wherein n represents 1 or 2), a phosphorus atom-containing compound (c) copper hydroxide Wherein RO is the general formula of 2 ## STR2 ## CH2 = C (X) COO ( Y) m - ( wherein, X is a hydrogen atom or a methyl group, Y 2 carbon atoms
4. The resin composition according to claim 1, which is a (meth) acryloyloxyalkyl group or a (meth) acryloylpolyoxyalkyl group represented by the following formula: 3. The resin composition according to claim 1, which has an average light transmittance of 50% at a wavelength of 450 to 650 nm.
As described above, the average light transmittance at 800 to 1000 nm is 20%.
A near-infrared absorbing material that is: