JPH04174403A - Abrasion resistant infrared ray absorbing filter produced by coating method - Google Patents

Abstract

PURPOSE:To obtain an infrared ray absorbing filter having both sufficient infrared ray absorbing ability and abrasion resistance by providing an abrasion resistant layer on an infrared ray absorbing layer. CONSTITUTION:Special copolymer solution is used as coating liquid 1 for forming an infrared ray absorbing layer, and the solution of compound which is a high solid matter and has an amide group or a nitrile group is used as a coating liquid 2 for forming an abrasion resistant layer to satisfy both abrasion resistance and infrared ray absorbing ability and moreover to form the filter having adhering ability. The coating liquid 1 is composed of acrylic ester and a compound having amid group, nitrile group or epoxy group of acrylic acid or metaacrylic acid. The coating liquid 2 is composed of the hydrolysis substance or partial condensate of alkoxysilane compound mixture, SiO powder, a compound having the amid group or nitrile group of acrylic acid or metakrill acid, and epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an infrared absorbing filter imparted with scratch resistance by a coating method.

Prior art and its problems In general, methods for imparting infrared absorbing properties include a kneading injection method and a coating method.

However, in the kneading injection method, the temperature of the resin to be kneaded is
It is necessary to raise the temperature above the decomposition temperature of the infrared absorber, which causes deterioration in the performance of the infrared absorber contained.

On the other hand, in the conventional coating method, this
When used in infrared absorption filters for devices, etc., due to the nature of the coating agent, it is not possible to effectively obtain the selective absorption property of the specific wavelength of the infrared absorption filter for CCD devices, and wavelengths other than the specific wavelengths are also absorbed. As a result, the CCD element that converts the optical signal into an electrical signal may send an erroneous signal.

Furthermore, as a means for imparting scratch resistance to an infrared absorption filter, a method of applying a hard coat to the surface of the filter has been conventionally known.

However, in the case of a corrugated hard coat, increasing its surface hardness reduces its adhesion to the support; on the other hand, in a two-component hard coat, its adhesion improves but its surface hardness decreases. It has the disadvantage of being

Therefore, there is a strong need for the development of a scratch-resistant infrared absorption filter that has both sufficient infrared absorption and scratch resistance.

Means for Solving the Problems As a result of extensive research in view of the above-mentioned problems of the prior art, the present inventors have discovered that scratch-resistant By using a solution of a compound with a high solid content and a hydroxyl group, an amide group, or a nitrile group as the coating liquid for forming the adhesive layer, it is possible to satisfy both scratch resistance and infrared absorption properties, and also provide adhesion. We discovered that it is possible to create filters based on

That is, the present invention provides the following scratch-resistant infrared absorption filter.

■ An infrared absorbing layer is provided on a transparent resin substrate.
A scratch-resistant infrared absorbing filter characterized in that a scratch-resistant layer is further provided on the infrared absorbing layer.

■ An infrared absorbing layer is provided on a transparent resin substrate.
A scratch resistant layer is further provided on the infrared absorbing layer,
The infrared absorbing layer contains (a) 60 to 90 parts by weight of at least one ester selected from methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate;
Hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, compounds having an amide group of acrylic acid, compounds having a nitrile group of acrylic acid, compounds having an epoxy group of acrylic acid , a compound having an amide group of methacrylic acid, a compound having a nitrile group of methacrylic acid, and a compound having an epoxy group of methacrylic acid (
A copolymer containing 10 to 40 parts by weight of each type in a total of 100 parts by weight, and (b) an infrared absorber consisting of an aminium type, a metal complex type, an anthraquinone type, and a diimonium type based on 100 parts by weight of the above copolymer. (1) R1Si(OR2)3 and 5i(OR3)4 (wherein R1 is a methyl group, an ethyl group, or a propyl group). ,R
2 is a methyl group, ethyl group or propyl group, R3 is
methyl group, ethyl group or propyl group) is 7.
2.5 to 10 parts by weight of SiO2 powder per 100 parts by weight of (i), (xtt) For 100 parts by weight of (1), 60 to 90 parts by weight of at least one ester selected from methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxy Propyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, compounds having an amide group of acrylic acid, compounds having a nitrile group of acrylic acid, compounds having an amide group of methacrylic acid, and compounds having a nitrile group of methacrylic acid 1.5 to 3.5 parts by weight of at least one copolymer selected from the group consisting of 10 to 40 parts by weight for a total of 100 parts by weight; (iv) epoxy resin for 100 parts by weight of (i); 0.75 to 2 parts by weight and (v) 0.75 to 2 parts by weight of curing catalyst per 100 parts by weight of (1).
A scratch-resistant infrared absorption filter characterized by comprising 25 to 1 part by weight.

The present invention will be explained in detail below.

First, the transparent resin substrate that can be used in the present invention only needs to have transparency, and examples thereof include known acrylic resins, methacrylic resins, and polycarbonate resins.

The infrared absorbing layer is made of at least one ester selected from methyl acrylate, ethyl acrylate, methyl methacrylate, and methyl methacrylate.
Weight parts and esters such as hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate,
Hydroxyethyl methacrylate, hydroxypropyl methacrylate, compounds with an amide group of acrylic acid, compounds with a nitrile group of acrylic acid, compounds with an epoxy group of acrylic acid, compounds with an amide group of methacrylic acid, compounds with a nitrile group of methacrylic acid A copolymer obtained by adding 10 to 40 parts by weight of at least one selected from the group consisting of a compound having an epoxy group and a compound having an epoxy group of methacrylic acid for a total of 100 parts by weight is used.

Specific examples of the above esters include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc. Specific examples of compounds having an amide group of acrylic acid include acrylamide, and compounds having a nitrile group of acrylic acid. Specific examples include acrylic acid nitrile, etc., specific examples of compounds having an amide group of methacrylic acid include methacrylic acid amide, and specific examples of compounds having a nitrile group of methacrylic acid include methacrylic acid nitrile, etc. I can do it.

Next, an infrared absorbing agent is added and mixed with the above copolymer.

As the infrared absorbing agent, at least one type of known infrared absorbing agent consisting of aminium type, metal complex type, anthraquinone type, and diimonium type can be used, and the amount added is 0.025 parts by weight per 100 parts by weight of the above copolymer. ~5 parts by weight.

Specific examples of the aminium-based infrared absorber include an aminium-based infrared absorber represented by the following structural formula [marketed as rKayasorb IRG-003J (manufactured by Nippon Kayaku Co., Ltd.)].

Examples of metal complex-based infrared absorbers include metal complex-based infrared absorbers rlRF-700J, rlRF-770'', rlR
F-860J, rIRF-880'', rIRF-905
Specific examples include those commercially available as J, rlRF-1000J, rIRF-1170J (all manufactured by Fuji Photo Film Co., Ltd.).

As anthraquinone-based infrared absorbers, JP-A-60-
Specific examples include those disclosed in No. 43605 and Japanese Patent Application Laid-open No. 62-246963.

As a diimonium-based infrared absorber, rIRG 0
22J (manufactured by Nippon Kayaku Co., Ltd.) can be exemplified as a specific example.

These infrared absorbers can be used alone or in combination of two or more.

A coating liquid can be obtained by adding an organic solvent to the above-mentioned copolymer mixed with an infrared absorber. The solid content of coating liquid I is preferably 5 to 15%.

As the above-mentioned organic solvent, known organic solvents can be used, such as ketones such as acetone, methyl acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, butylon, methyl amyl ketone, and methyl amyl ketone, methyl ether, ethyl ether, and isopropyl ether. , ethers such as methyl cellosolve, methyl carpitol, anisole, tetraethylene glycol dimethyl ether, propylene oxide, dioxane, tetrahydrofuran, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tertiary amyl alcohol, n-octyl alcohol, Examples include alcohols such as ethylene glycol, benzyl alcohol, cyclohexanol, and tetrahydrofurfuryl alcohol.

Coating liquid I obtained as above is applied onto the transparent resin substrate to a film thickness of about 0.5 to 1.5 μm, and dried at about 60 to 90°C for about 10 to 20 minutes.・Harden.

Next, the copolymer used in coating liquid H for forming a scratch-resistant layer on the infrared absorbing layer is methyl acrylate, ethyl acrylate, 60 to 90 parts by weight of at least one selected from esters consisting of methyl methacrylate and ethyl methacrylate; and 60 to 90 parts by weight of at least one ester selected from esters consisting of methyl methacrylate and ethyl methacrylate; A total of 100 parts by weight of at least one selected from the group consisting of a compound having an amide group, a compound having a nitrile group of acrylic acid, a compound having an amide group of methacrylic acid, and a compound having a nitrile group of methacrylic acid. It is produced by polymerizing parts by weight.

The polymerization regulator used at this time can be any known one, such as dodecyl mercaptan, and the polymerization initiator can be any known one, such as azobisisobutyronitrile. be able to.

-Also, a coating liquid to form a scratch-resistant layer■
The raw materials for the hydrolyzate and partial condensate of alkoxysilane compounds used in Using a mixture of an alkoxysilane compound with an ethyl group or a propyl group (R3 is a methyl group, an ethyl group, or a propyl group), R' S i (OR2)3 and S i (OR3
)4 is set at a molar ratio of 7:3 to 10:0.

On the other hand, regarding SiO2 powder, 20 to 40% by weight of SiO2 powder is dispersed in an organic solvent such as alcohol to form a silica sol, and a mixture of this and the above-mentioned alkoxysilane compound is mixed in an acidic aqueous solution such as hydrochloric acid at about 20 to 30 ° C. for about 45 minutes. Stir and perform hydrolysis. In addition, in the case of partial condensation, the above hydrolyzate is heated at 50°C for 3 hours and stirred,
A partial condensate is obtained. In addition, the particle size of the SiO2 powder is 5~
It is preferable to set it to 30 micrometers.

The above copolymer, epoxy resin, curing catalyst, and leveling agent were added to the product obtained above, and the mixture was stirred in an acidic aqueous solution such as acetic acid at room temperature for about 30 to 60 minutes, and the solid content was removed with an organic solvent. Adjust the solid content to 20 to 30% and use it as coating liquid (2).

As the above-mentioned epoxy resin and curing catalyst, known ones can be used, and as additives, in addition to the above-mentioned δ leveling agent (silicone oil), surfactants and the like can be used as necessary.

In addition, the content of each component in the coating solution (1) is 10% of the hydrolyzate and partial condensate of the alkoxysilane compound described above.
0 parts by weight, 2.5 to 10 parts by weight of SiO2 powder, 1.5 to 3.5 parts by weight of the above copolymer, 0.75 to 2 parts by weight of epoxy resin, and 0.25 to 1 part by weight of curing catalyst. Department.

Next, on the transparent resin substrate on which the infrared absorbing layer was provided with coating liquid I, coating liquid ■ is applied to a film thickness of 3 to 3.
Coat to a thickness of 6 μm and heat at 80 to 120°C for 1 to 6 μm.
Let dry and harden for about 2 hours. The above coating method may be carried out using conventional methods such as coating and dipping for both coating solutions.

Effects of the Invention According to the scratch-resistant infrared absorption filter of the present invention, the surface hardness of the scratch-resistant layer is high, so it is difficult to get scratched and does not impede the incidence of light.

In addition, since the infrared absorbing layer is mainly composed of a polymer, the performance of the infrared absorbent is not impaired due to thermal decomposition, etc., and the selectivity of specific wavelength absorption can be increased.
Moreover, since the substrate and the infrared absorbing layer and the infrared absorbing layer and the scratch-resistant layer are in close contact with each other, the functional effects of both the infrared absorbing layer and the scratch-resistant layer can be sufficiently obtained, and as a result, the present invention Products using scratch-resistant infrared absorption filters can exhibit excellent functionality, reliability, durability, and flexibility.

EXAMPLES Examples will be shown below to further clarify the features of the present invention.

Example 1 (1) Production and operation of coating liquid I (a) Synthesis of copolymer 142 g of methyl methacrylate, 36 g of 2-hydroxyethyl methacrylate, 0.15 g of polymerization modifier dodecyl mercaptan and 118 g of MEK were added to the fourth batch. Place in a flask, attach a condenser, stirrer and thermometer, and add 0% of the polymerization initiator azobisisobutyronitrile in the presence of nitrogen gas.
．． 15 g was added and polymerized. Continuing the reaction while adding an organic solvent as necessary, the solid content is 31% and the viscosity is 980.
A copolymer of c ps was obtained.

・Operation (b)...Manufacturing operation of coating liquid I (a)
An organic solvent was further added to the copolymer obtained in step 1 to obtain a predetermined solid content, and further a metal complex-based infrared absorber rlRF7 was added.
0.172 g of 0.00J (manufactured by Fuji Photo Film Co., Ltd.) was added and mixed to obtain a coating liquid (2) with a solid content of 9.0%.

(ii) Production and operation of coating liquid H (c) Synthesis of copolymer 142 g of methyl methacrylate, 36 g of 2-hydroxyethyl methacrylate, 0.15 g of polymerization modifier dodecyl mercaptan, 27 g of SMEK, and 9 g of dioxane
1 g was placed in a four-eye flask, a condenser, a stirrer, and a thermometer were attached, and 0.15 g of azobisisobutyronitrile, a polymerization initiator, was added in the presence of nitrogen gas for polymerization. Continue the reaction while adding an organic solvent as necessary to reduce the solid content to 35
%, and a viscosity of 8000 cps was obtained.

・Operation (d)...Manufacture of coating liquid ■0.02N
85 g of -HCρ aqueous solution and 46 g of IPA silica sol were placed in a four-eye flask and cooled to below 30°C. A mixed solution of 189 g of methyltriethoxysilane and 48.1 g of tetramethoxysilane was added dropwise to the mixture while cooling for about 45 minutes to cause hydrolysis, followed by stirring at 50° C. for 3 hours to obtain a partial condensate.

Next, 19.6 g of acetic acid, 92.7 g of the copolymer obtained in step (c), 1.1 g of a leveling agent, 3 g of an epoxy resin, and 1.4 g of a curing catalyst were added to this, and the mixture was sufficiently stirred to reduce the solid content. A 24.9% coating solution (■) was obtained.

(Hi) Application of coating liquid I and ■ - A square piece of length 50aug, thickness 2111ffl transparent resin substrate was immersed in coating liquid I, and the pulling speed was 0.4cm/
See the coating, immediately dry at 90° C. for 15 to 45 minutes, and allow to cool.

Next, the above transparent resin substrate was immersed in the coating liquid (2), coated at a pulling rate of 0.4 cm/see, and immediately
By drying and curing at 10° C. for 2 hours, an infrared absorption filter with scratch resistance was obtained.

(1v) Evaluation method Regarding the scratch-resistant infrared absorption filter obtained above,
Its scratch resistance, adhesion, hot water resistance and spectral properties were investigated. The results are shown in Table 5.

Each evaluation method is shown below.

A) Scratch resistance...1k with #000 steel wool
The evaluation was based on the number of scratches when the sample was reciprocated 10 times under a load of g.

The number of scratches is expressed as follows.

Good: Number of scratches: 0 to 2 Normal: Number of scratches: 3 to 5 Poor: Number of scratches: 6 or more B) Adhesion: Cross cut (IOXIO) at 1 mm intervals with a cutter knife Evaluation was made based on the number of films remaining when a cellophane tape (Cellotape J No. 405 manufactured by Chiban Co., Ltd.) having a width of 18 mm was peeled off the substrate 5 times. The number of remaining films is expressed as follows.

Good...Film remaining 100/100 Normal...Film remaining 90-99/100 Poor...Film remaining 89 or less/100 C) Hot water resistance...When immersed in 80℃ hot water for 30 minutes The presence or absence of any abnormalities was investigated. This evaluation method is based on B) above.
A cross-cut test method was applied.

D) Spectral characteristics...Check the spectral characteristics for each,
Its spectral characteristic diagram is shown.

E) Appearance: The presence or absence of bubbles, cloudiness, whitening, unevenness, etc. was examined.

Examples 2 to 17 Composition of the copolymer obtained in operation (a), composition of coating liquid I obtained in operation (b), composition of the copolymer obtained in operation (c), and composition of the copolymer obtained in operation (d) Tables 1, 2, 3, and 4 show the compositions of the coating liquids I and II, respectively, and scratch-resistant infrared absorption filters (sample Nos. 2 to 17) were prepared by changing the combinations of coating liquids I and ■.
) was created. The same operations as in Example 1 were performed except for the composition shown in each table above. Furthermore, in Tables 1 to 4,
The solid content and viscosity of each composition are also shown.

Further, the scratch-resistant infrared absorbing filter obtained by combining coating liquids I and H was also tested using the same evaluation method as in Example 1. The combinations and test results are shown in Table 5. Incidentally, the spectral characteristic diagrams of samples Nos. 1O to 17 in Table 5 had the same results as in FIG. 9.

Table 2

[Brief explanation of drawings]

FIG. 1 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample N0I) obtained in Example 1. FIG. 2 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 2) obtained in Example 2. FIG. 3 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 3) obtained in Example 3. FIG. 4 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 4) obtained in Example 4. FIG. 5 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample N05) obtained in Example 5. FIG. 6 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 6) obtained in Example 6. FIG. 7 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 7) obtained in Example 7. FIG. 8 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 8) obtained in Example 8. FIG. 9 is a spectral characteristic diagram of the scratch-resistant infrared absorption filter (sample No. 9) obtained in Example 9. (Above) Figure 1 5 Skin surface (nm) Figure 2 S anti-t (nm) Procedural amendment blind motion) February 25, 1991 Commissioner of the Japan Patent Office Satoshi Ue Matsu Indication of case 1 Patent application filed in 1990 No. 303241 No. 2 Name of the invention Scratch resistance by coating method Infrared Japan Aspherical Lens Co., Ltd. 4 Agent 2-1-2 Hirano-cho, Chuo-ku, Osaka Sawanotsuru Building fi06
(203) 0941 February 12, 1991 6 Contents of amendment in the section “Detailed Description of the Invention” in the specification subject to amendment 1, page 4 of the specification, lines 6 to 7 [Scratch resistant infrared absorption filter. ] followed by a new line and “Detailed description of the invention”
join. (that's all)

Claims (1)

[Scope of Claims] [1] A scratch-resistant infrared-absorbing filter, characterized in that an infrared-absorbing layer is provided on a transparent resin substrate, and a scratch-resistant layer is further provided on the infrared-absorbing layer. [2] An infrared absorbing layer is provided on a transparent resin substrate, an abrasion resistant layer is further provided on the infrared absorbing layer, and the infrared absorbing layer comprises (a) methyl acrylate, ethyl acrylate, 60 to 90 parts by weight of at least one selected from esters consisting of methyl methacrylate and ethyl methacrylate, and hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and acrylic acid. Compounds having an amide group of acrylic acid, compounds having a nitrile group of acrylic acid, compounds having an epoxy group of acrylic acid, compounds having an amide group of methacrylic acid, compounds having a nitrile group of methacrylic acid, and compounds having an epoxy group of methacrylic acid. A copolymer containing 10 to 40 parts by weight of at least one selected from the group consisting of compounds, and (b) 100 parts by weight of the above copolymer, aminium-based, metal complex-based, anthraquinone-based, and At least one selected from dimonium-based infrared absorbers.
(i) R^1Si(OR^2)_3 and Si(OR^3)
_4 (However, R^1 is a methyl group, ethyl group or propyl group, R^2 is a methyl group, ethyl group or propyl group, R^3 is a methyl group, ethyl group or propyl group)
Hydrolyzate and partial condensate of a mixture of alkoxysilane compounds having a molar ratio of 7:3 to 10:0, (ii) 2.5 to 10 parts of SiO_2 powder per 100 parts by weight of (i); parts by weight, (iii) 60 to 90 parts by weight of at least one ester selected from esters consisting of methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, and hydroxymethyl acrylate, based on 100 parts by weight of (i); , hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate,
selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, a compound having an amide group of acrylic acid, a compound having a nitrile group of acrylic acid, a compound having an amide group of methacrylic acid, and a compound having a nitrile group of methacrylic acid 1.5 to 3.5 parts by weight of at least one copolymer, 10 to 40 parts by weight, for a total of 100 parts by weight; (iv) 100 parts by weight of (i), 0 parts of epoxy resin;
．． 75-2 parts by weight and 0.25 parts by weight of curing catalyst for 100 parts by weight of (v)(i)
1 part by weight.