AU608984B2 - Color filter - Google Patents

Description

V

14, 608984

COMPLETE

Application Number: Lodged:

SPECIFICATION

FOR OFFICE USE Class Int. Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: This document contains the h kfendme;.ts allowed under Section 83 by the Supervising Examiner on and is correct for printing L -Lj^ Sa 00 o o 04 a 0 00 0 0 0 a o 0 e o« TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Inventors: Address for Service: MITSUI PETROCHEMICAL INDUSTRIES, LTD.

2-5, Kasumigaseki 3-chome, Chiyod-ku, Tokyo 100, Japan.

Kakutaro KAUCHI and Toru TOMOSHIGE SMITH SHELSTON BEADLE 207 Riversdale Road Box 410) Hawthorn, Victoria, Australia Complete Specification for the invention entitled: COLOR FILTER The following statement is a full description the best method of performing it known to us: of this invention, including Page 1 Our Ref: #3556 PS:MW:WB It- 1 i

I.

0 la This invention relates to color filters mounted in optical instruments or on the outer surface of a display panel of cathode ray tubes or liquid crystal displays and effective in protecting against electron beams or improving 5 the tone of the display panel, and more particularly, to color filters comprising a transparent substrate of heat resistant, highly transparent, chemical resistant thermosetting plastic material.

Prior art color filters use transparent substrates o formed of glass and polyester resins.

The glass substrates suffer from the drawbacks of low impact resistance and heavy weight.

04 We 9 S0 0 0 0 00 00 0 0 00 S000 0 0 0 00 0 0 0 0 00 0 0000 a 0 00 0 SAMMARY OF THE INVENTION 00o, An object of the present invention is to provide a S 15 color filter having improved chemical, solvent, heat and So.'o weathering resistance, and high transparency and substantially free from birefringence.

According to the present invention, there is provided a color filter comprising a transparent substrate of a polymer of a polymerizable liquid composition containing a monomer or an oligomer or a mixture thereof containing a diallyl compound as an essential component.

Preferably, the diallyl compound is a bis(allyl carbonate) of an aliphatic, cycloaliphatic or aromatic dihydric alcohol.

Preferably, the polymer is shaped and then subjected to at least one treatment selected from corona discharge, chromate and burning treatments.

I y 1*_ [4i~

I

I--

A 'e 2 The present invention also provides a color filter comprising a transparent substrate which is formed from a copolymer of a polymerizable liquid composition containing a momoner or an oligomer or a mixture thereof containing a diallyl compound as an essential component and an unsaturated carboxylic acid or a derivative thereof.

a oPreferably the invention provides a color filter a S color filter comprising a transparent substrate and a colored 0 0 0 O" coating or a layer disposed on said transparent substrate, 0 0 K0 said transparent substrate comprising a polymer of a 00 00 0 0o0. polymerizable liquid composition containing a monomer or an 00 0 o oligomer or a mixture thereof containing a diallyl compound as an essential component, having a general formula: 0. 0 00000 oo" CH 2

=CH-CH

2 [R-0-C-O]n-CH 2

-CH=CH

2 Oo o 00 0 wherein R is a residue of a dihydric alcohol, and n has a 0 900000 value of an average value in the range of from 1 to 10, and said transparent substrate being imparted with an DO0 0000 oo' affinity for the colored coating or layer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a color filter according to one embodiment of the present invention.

FIG. 2 is a cross-sectional view of a color filter according to another embodiment of the present invention.

FIG. 3 is a cross-sectional view of a color filter according to a further embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in further detail referring to the preferred embodiments shown in the jbspe.003/mitsu 91 1 7 x, 9 'V t' 1 -1 Referring to FIGS. 1 to 3, the color filter of the invention comprises a transparent substrate 1 which may be of any structure as long as it is formed from a polymer of a polymerizable liquid composition containing a monomer or an oligomer or a mixture thereof containing a diallyl compound as an essential component.

Some exemplary structures of the color filter of the 00 0 009 0 O a D o 0 invention are shown in the cross-sectional views of FIGS. 1 to S0 0 oo0 3 0 0 0 0o FIG. 1 illustrates a color filter comprising a 0 0 0 0 transparent substrate 1 and a colored topcoat 2 formed on one 0O 00 00 0 0 9 surface thereof as by printing.

FIG. 2 illustrates a color filter comprising a o0.eeo transparent substrate 1 and a layer 3 having a colored pattern 0 a I laminated on one surface thereof.

a o o 0 4 jbspe.003/mitsu 91 1 7 4: .1 ar ~a C i~ ll-i li- l~a^ll U W ~*L~L~L-LII- i FIG. 3 illustrates a color filter comprising a transparent substrate 1 which itself has a colored pattern.

The color filter of the invention is characterized in that the transparent substrate 1 is formed from a specific polymer, more illustratively, a polymer of a polymerizable liquid composition containing a monomer or an oligomer or a mixture thereof containing a diallyl compound as an essential component.

The diallyl compound is preferably a bis(allyl carbonate) of an aliphatic, cycloaliphatic or aromatic dihydric alcohol, more preferably a composition comprising a monomer or an oligomer or a mixture thereof of a 0, bis(allyl carbonate) of an aliphatic, cycloaliphatic or S0oo aromatic dihydric alcohol having the general formula: 0000 00 0 0°o 15 CH2=CH-CH2-0-C-0- H2-CH=CH2 o 0 0 n 00 00 00 0 0 o wherein R is a residue of a dihydric alcohol, and n has a 0.0 value or an average value in the range of from 1 to oo o preferably from 2 to 0 00 o oo Preferred component is the reaction product of 0 20 diallyl carbonate and a dihydric alcohol in a molar ratio of 0 0 0 0o.. 4:1 or lower, more preferably in a molar ratio of 2:1.

Preferred examples of the dihydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6oo o hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylpentane diol, cyclohexane dimethanol, bis(hydroxymethyl)tricyclodecane, 2,7-norbornane diol, a,a'-xylene diol, 1,4-bis(hydroxyethoxybenzene), and 2,2-bis[4-(hydroxyethoxy)phenyl]propane alone and mixtures thereof.

The composition which is to be polymerized into the polymer of which the transparent substrate 1 of the color filter of the invention is formed is preferably a liquid *i

*CI

44 4 composition comprising components and shown below. Reference is made to Japanese Patent Application Kokai No. 59-140214, which is incorporated herein by reference.

The preferred liquid composition comprises 10 to 90% by weight of an oligomer or a mixture of oligomers of a bis(allyl carbonate) of an aliphatic, cycloaliphatic or aromatic dihydric alcohol having the general formula:

SCH

2

=CH-CH

2 C-0--R-O-C-0-CH 2

-CH=CH

2 i f I 0 0 0 n wherein R is a residue of a dihydric alcohol, and n has a J- value or an average value in the range of from 1 to especially 2 to 10, with the proviso that the content of a H dihydric alcohol bis(allyl carbonate) monomer optionally present in the oligomer is up to 50% by weight; 0 to 90% by weight of a compound selected from the o 'o group consisting of a monomeric di- or tri(allyl carbonate) of an aliphatic, cycloaliphatic or aromatic di- or trihydric alcohol having the general formula: R' 0-C-O-CHa- CHCH2 So 0 n wherein R' is a residue of a di- or trihydric alcohol, and n' is equal to 2 or 3, or a mixture thereof, with the proviso that the content of an oligomeric bis(allyl carbonate) of a di- or trihydric alcohol or a poly(allyl carbonate) of a dior trihydric alcohol optionally present in the monomer or the |N mixture is up to 30% by weight, an allyl ester of an S e. aliphatic or aromatic di- or tricarboxylic acid having the 77 general formula:

X

i c

R"-C-O-CH

2

-CH=CH

2 11 0 wherein R" is a residue of a di- or tricarboxylic acid, and n" is equal to 2 or 3, and triallyl cyanurate and triallyl isocyanurate; and 0 to 30% by weight of an acrylic or vinyl monomer; with the proviso that the total of components and is nore than 0.

The preferred component is the reaction product of diallyl carbonate and a dihydric alcohol in a molar ratio of S 4:1 or lower, more preferably in a molar ratio of 2:1. The dihydric alcohol is preferably selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butane- S. diol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, 0 0 Q 000 dipropylene glycol, propylene glycol, neopentyl glycol, 0 15 trimethylpentane diol, cyclohexane dimethanol, di(hydroxymethyl)tricyclodecane, 2,7-norbornane diol, a,a'-xylene diol, 0040 S0 1,4-bis(hydroxyethoxybenzene), and 2,2-bis[4-(hydroxyethoxy)- 00 phenyl]propane.

0 The preferred component is the reaction product of 0 00 4 Z 0 diallyl carbonate and a di- or trihydric alcohol in a molar ratio of 6:1 or higher, more preferably in a molar ratio of 12:1. The di- or trihydric alcohol is preferably selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, propylene glycol, neopentyl glycol, trimethylpentane diol, cyclohexane dimethanol, bis(hydroxymethyl)tricyclodecane, 2,7-norbornane diol, a,a'-xylene diol, 1,4-bis(hydroxyethoxybenzene), 2,2bis[4-(hydroxyethoxy)phenyli]propane, trimethylol propane, and tri(hydroxyethyl) isocyanurate alone and mixtures thereof.

i 1 .4 6 Also included in component are diallyl phthalate, diallyl succinate, diallyl adipate, diallyl chlorendate, diallyl glycolate, diallyl naphthalene dicarboxylate, and triallyl mellitate.

Component is preferably selected from vinyl acetate, vinyl benzoate, methyl methacrylate, phenyl methacrylate, methyl acrylate, methyl maleate, maleic anhydride, and vinylidene chloride alone and mixtures thereof.

Other examples of the aliphatic, cycloaliphatic or aromatic dihydric alcohol bis(allyl carbonate) which may be used in the present invention include o 0f S' a copolymerizable composition comprising a diallyl ester of a nuclearly halo-substituted benzene dicarboxylic 000 15 acid and diethylene glycol diallyl carbonate as disclosed in o 0 0o Japanese Patent Application Kokai No. 59-45312; o [II] a copolymerizable composition comprising at least one nuclearly halo-substituted benzene dicarboxylic acid o 0 o e ester (for example, bisallyl 2,4-dichloroterephthalate) and 2o at least one radical-polymerizable monofunctional monomer o o bearing an aromatic ring and capable of forming a homopolymer Do having a refractive index of at least 1.55 (for example, phenyl methacrylate) as disclosed in Japanese Patent o 00 0o0e* Application Kokai No. 59-8709; [III] a copolymerizable composition comprising at least Sone bisallyl carbonate or bis- -methylallyl carbonate (for 0000 o* 0 example, 1,4-bis(hydroxyethoxy)benzene bisallyl carbonate) and at least one radical-polymerizable monofunctional monomer bearing an aromatic ring and capable of forming a homopolymer ?0 having a refractive index of at least 1.55 (for example, phenyl methacrylate) as disclosed in Japanese Patent Application Kokai No. 59-8710; [IV] a copolymerizable composition comprising a monomer obtained by reacuing a monool (for example, 4-benzyl-phenol) with an unsaturated carboxylic acid or chloride thereof (for

I--F

uu~~~ 7 example, acrylic acid or chloride thereof) and a radicalpolymerizable monomer capable:of forming a homopolymer having a refractive index of at least 1.55 (for example, styrene) as disclosed in Japanese Patent Application Kokai No. 59-96109; a copolymerizable composition comprising a chlorobenzoic acid allyl ester (for example, 2,3dichlorobenzoic acid diallyl ester) and a difunctional monomer (for example, tetrabromophthalic acid diallyl ester) as disclosed in Japanese Patent Application Kokai No. 59to 96113; [VI] a copolymerizable composition as disclosed in Japanese Patent Application Kokai No. 59-184210; [VII] diethylene glycol bisallyl carbonate; and S[VIII] a composition comprising a bisally compound such 15 as diethylene glycol bisally carbonate, 1,4-bis(hydroxy- 44 4 *i ethoxy)benzene bisallyl carbonate, 2,4-dichloroterephthalic S*0o acid bisally ester and a vinyl monomer bearing an aromatic ring such as phenyl methacrylate and benzyl methacrylate.

In preparing a polymer from a polymerizable liquid composition containing a monomer or an oligomer or a mixture thereof containing a diallyl compound as an essential t 4, component to form a transparent substrate according to the present invention, an unsaturated carboxylic acid and/or a t It 'tct derivative thereof may be copolymerized therewith.

This copolymerization reaction may be carried out either at an initial stage along with the oligomer or other t components of the polymerizable liquid composition or after polymerization reaction of the polymerizable liquid composition has taken place to a certain extent.

The unsaturated carboxylic acids and derivatives thereof which may be copolymerized with the polymerizable liquid composition in the practice of the present invention include a,3-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic S3 acid, citraconic acid, tetrahydrophthalic acid, etc.; I "I.I Pf 8 unsaturated carboxylic acids such as bicyclo[2.2.1]hept-2ene-5,6-dicarboxylic acid; a,P-unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, etc.; unsaturated carboxylic acid anhydrides such as bicyclo- [2.2.1lhept-2-ene-5,6-dicarboxylic anhydride; and unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, i0 tetrahydrophthalic anhydride dimethyl ester, dimethyl bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate, etc. Preferred among them are maleic acid, bicyclo[2.2.1]hept-2-ene-5,6dicarboxylic acid or anhydride, and methacrylic acid.

The amount of the unsaturated carboxylic acid and/or i5 derivative thereof used may vary, but is generally from 0.01 I to 20 parts by weight, preferably from 0.1 to 10 parts by S weight, more preferably from 0.5 to 10 parts by weight per 100 parts by weight of the polymerizable liquid composition aa aa containing a monomer or an oligomer or a mixture thereof containing a diallyl compound as an essential component.

S'a In the practice of the present invention, StI copolymerization of such an unsaturated carboxylic acid Sand/or a derivative thereof with the above-defined s. lt polymerizable liquid composition results in a copolymer having good affinity to printing ink, with the advantage that forming a transparent substrate from the copolymer provides a S' transparent color filter having good affinity to printing ink and improved chemical, heat and weathering resistance.

The polymerizable liquid composition may further contain another monomer and a filler in such amounts that they do not deleteriously affect the physical properties of the resulting polymer. For example, a mono (meth)acrylic compound, di(meth)acrylic compound, or unsaturated carboxylic acid such as maleic anhydride may be added in an amount of up to 30% by weight, or a silane coupling agent such as vinyl It- i I 9 triethoxysilane may be added in an amount of up to 10% by weight, based on the weight of the polymer.

Transparent substrates may be obtained by polymerizing these polymerizable liquid compositions or copolymerizable compositions containing such a polymerizable liquid composition and an unsaturated carboxylic acid or a derivative thereof, for example, by adding a polymerization initiator to composition or as mentioned above or a similar composition further containing another monomer and filler, casting the composition into a mold having a polished cavity surface which is formed from a mold material having excellent smoothness such as glass, and effecting in situ polymerization into a plate.

S' The polymerization initiator used herein may be any of 15 photo polymerization initiators, thermal polymerization 0, at initiators, and photo and thermal polymerization initiators.

o a' The photo polymerization initiators include electron beam and radiation polymerization initiators as well as photo 4 polymerization initiators.

A typical example of the photo polymerization initiator is 2-hydroxy-2-methyl-l-phenyl-propan-l-one.

0 tO IExamples of the thermal polymerization initiators Sinclude peroxydicarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and tert-butyl perbenzoate; organic peroxides such as benzoyl peroxide, acetyl peroxide, tertbutyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide, diisopropyl peroxydicarbonate, dimethyl ethyl ketone I3 peroxide, and diacyl peroxide; and radical initiators such as azobisisobutyronitrile and azobismethylisovaleronitrile.

A typical example of the photo and thermal polymerization initiators is the compound of the following formula: Mon 1~10 00 0 (t-Bu) -00-C C CG-(-u tj -00 CG-(-u 0 0 The polymerization initiator may be used in an amount of 0.1 to 10% by weight, preferably 1 to 6% by weight based on the polymerizable liquid composition.

Polymerization may be carried out under various conditions. In the case of thermal polymerization, for to exam-ple, the composition may be heated in a heating tank to a temperature of about 30 to 150'C, preferably about 40 to C 120'C for about 1/2 to 72 hours, preferably about 1 to 4 hours, although the exact value will vary with the shape and 0100 size. In the case of photo polymerization, polymerization :15 mE- 1 be carried out under a high-pressure mercury lamp with a 0 4040 power of 60 to 150 W/cm for about 1 minute to 2 hours, preferably 3 to 30 minutes at a temperature of about 40 to a 120'C, preferably about 60 to 100'C.

Polymerization of copolymerizable composition (2) 004 'o containing a polymerizable liquid composition as defined above and an u-saturated carboxylic acid or a derivative thereof may be carried out at a temperature of 30 to 100'C for 1/2 to 20 hours.

In the practice of the present invention, the composition is polymerized and molded into a transparent substrate preferably having a thickness of 10 pim to 5 mm, especially 50 .tm to 2 mm.

In the practice of the present invention, the thus molded substrate is surface treated through a corona discharge, chromate or burning treatment or a combination thereof. Then the adhesion between the transparent substrate surface and a topcoat such as ink is improved when the I. transparent substrate is to be subsequently printed with ink or laminated with a colored layer into a color filter.

12 The transparent substrate formed from a polymer of the above-defined polymerizable liquid composition or a copolymer of the same liquid composition with an unsaturated carboxylic acid or a derivative thereof has the following optical, chemical and physical properties.

The transparent substrate exhibits minimized double refraction to both perpendicular and oblique incident light even when it is up to 1.0 mm thick.

The transparent substrate well transmits light of the entire visible light spectrum so that the color of ink is fixed without a change.

Since the transparent substrate has improved weathering and ultraviolet radiation resistance, it can be printed with a ultraviolet radiation-curable ink composition which "0 15 requires exposure to a high energy of ultraviolet radiation.

0 Since the transparent substrate has improved heat O0° resistance, it can be printed with a thermosetting ink 00 0 e composition which requires elevatec temperatures or a 0ultraviolet radiation-curable ink composition which is to be heated upon exposure to heat radiation.

The transparent substrate has an increased ability to i' bind ink.

Since the transparent substrate has improved chemical and solvent resistance, it is not deleteriously affected by 2$ liquid crystal and polyimides.

The transparent substrate has increased surface hardness and improved abrasion resistance, which leads to ease of operation upon application.

The transparent substrate allows a transparent ja electrode to be formed thereon. The adhesion between the color filter and the transparent electrode is further enhanced when the transparent substrate is printed with ink and then pretreated on the surface with a silicone base hard coating prior to formation of the electrode.

12 Generally, a color filter is obtained by forming a colored coating or layer on the transparent substrate according to the present invention. Alternatively, a color filter may be fabricated by incorporating an adequate pigment into a polymer during polymerization to thereby directly color the resulting transparent substrate.

The colored coating is generally formed by coating or printing a color paste onto the transparent substrate although the method of forming :he color filter of the present invention is not limited thereto.

The color paste which is used to coat the color filter includes polyimide and acrylic varnish compositions having o o pigments added thereto. If desired, a pattern may be formed S; 3 in the pigmented resin layer by applying thereon a positive 0 0 0 JS or negative photoresist, forming a photoresist pattern, and Oo o; etching the resin layer through the masking photoresist o0o pattern.

0 0 The use of a photosensitive polyimide precursor as the 00 a o color paste makes it possible to form a pattern by directly 0 etching the photosensitive polyimide precursor without a 00 0 o 5 photoresist.

o o, One example of the photosensitive, heat-resistant, 0 color paste which is used to coat the color filter is a o at O. composition comprising a photosensitive polyimide precursor, a solvent, and an organic pigment insoluble in the solvent.

0° 0 More illustratively, photosensitive polyimide precursors are polymers as shown below to which a photosensitive group is attached through a chemical bond or with which a photosensitive compound is admixed.

Examples of polymer include polyamic acids synthesized by reacting: pyromellitic dianhydride with 4,4'-diaminodiphenyl ether, c 4e oc lc ii oll 13 pyromellitic dianhydride and 4,4 '-benzophenone tetracarboxylic dianhyciride with 4,4'-diaminodiphenyl ether, 3,31,4,41 -benzophenone tetracarboxylic dianhydride with 4, 4 -diaminodiphenyl ether, 3,3',4,4'-biphenyl tetracarboxylic dianhydride with 4, 4'-diaminodiphenyl ether, -biphenyl tetracarboxylic dianhydride and 4,4 '-benzophenone tetracarboxylic dianhydride with 4,4'diaminodiphenyl ether; pyromelJlitic dianhydride with 3,3'-diaminodipheny.

sulfone, 0 enpyrornellitic dianhydride and 3,3',4,4 '-benzophenone 0 01 tetracarboxylic acid dianhydride with or 4,4'-diaminoo diphenyl sulfone, 3,3',4,4'-benzophenone tetracarboxylic dianhydride with o3,3'- or 4,4'-diaminodiphenyl sulfone, 0 V"O 4,4' -bipheny. tetracarboxylic dianhydride with or 4,4'-diaminodipheny. sulfone, oQ 0 0 0 IQ 3 31,4 4'-benzophenone tetracarboxylic dianhydride with 3,3'- Go 4 or 4,4'-diaminodiphenyl sulfone; 00014pyromellitic dianhydride with 4,4' -diaminodipheny.

ether and bis(3-aminopropyl)tetratnethyldisiloxane, pyromeJllitic dianhydride and 4,4 '-benzophenone tetracarboxylic dianhydride with 4,4'-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane, 'Ig C 3,3 4,4' -benzophenone tetracarboxylic dianhydride with 4,4'-diaminodipheny. ether and bis (3-aminopropyl) tetramethyldisiloxane, 3,3',4,4'-biphenyl tetracarboxylic dianhydride with 4, 4'-diaminodiplienyl ether and bis (3-aminopropyl) tetramethyldisiloxane, 3,3',4,4'-biphenyl tetracarboxylic dianhydride and 4,4 '-benzophenone tetracarboxylic dianhydride with 4,4'-

I

4 .4 14 diaminodiphenyl ether and bis(3-aminopropyl)tetramethyldisiloxane; pyromellitic dianhydride with or 4,4'-diaminodiphenyl sulfone and bis(3-aminopropyl)tetramethyldisiloxane, pyromellitic dianhydride and 3,3',4,4'-benzophenone tetracarboxylic dianhydride with or 4,4'-diaminodiphenyl sulfone and bis(3-aminopropyl)tetramethyldisiloxane, 3,3',4,4'-benzophenone tetracarboxylic dianhydride with or 4,4'-diaminodiphenyl sulfone and bis(3-aminopropyl)tetramethyldisiloxane, 3,31,4,4'-biphenyl tetracarboxylic dianhydride with or 4,4'-diaminodiphenyl sulfone and bis(3-aminopropyl)tetramethyldisiloxane, 3,3',4,4'-biphenyl tetracarboxylic dianhydride and 0 00 3,3',4,4'-benzophenone tetracarboxylic dianhydride with 3,3'or 4,4-diaminodiphenyl sulfone and bis(3-aminopropyl)- 060 tetramethyldisiloxane; and the like.

0 0 0 Preferred examples of the photosensitive group (1-b) 0 a include groups having a vinyl, acryl, methacryl, allyl, or S 0 methallyl group. These photosensitive groups may be attached to the polyimide polymer precursors through an ester, amide, imide or similar linkage.

Such a photosensitive group may be introduced through an ester linkage by any well-known method, for example, by 2S the method disclosed in U.S. Patent No. 3,957,512.

Photosensitive compounds include bichromates, bisazides, vinyl-bearing amino compounds, azide-bearing amino compounds, or the like.

Such a polyimide polymer precursor can be made Z0 photosensitive by blending a bichromate salt therein by the method found by Kevwin and Coldrick (see Polymer Eng. Sci., 11, 426, 1971).

Typical examples of the bisazides are aromatic bisazides as given below.

0 N 3 CH

CH-

0 00 0 0 00 00 00 0 0 c 0 00 3 0 0 0 0 0 0 0 0 0 0 0 0 00 00 00 0 0 0 0 0 0000 0. 0 3 0 0 0 00 0 0 00 0o 0 00 0 N 3 -CH ~N 3 N 3 C H=CH// N 0

N

3

N

3

N

3 C =CH C CH=

-<N

0 0 0. '0 00 0 I 4 27

I

Illustrative examples of the vinyl-bearing amino compounds are given below.

/C H3

CH

2 =C CH 2

CH

3

COOCH

2

CH

2

N

CH

2

CH

3

CH

2 =CH CH 3 COOCH1 2

CH

2

N

C H 3 0 0 000 0 0 0 0.0 0 0 0 0 a 04' I 4 I

((C

C' V

CH

2 =CH CH 2 CHl 3

COOCH

2

CH

2

N

CH

2

CH

3

CH

3 C H 2 =C C O O C H 2 C H 2 N C A

(CH

3 2 C H 3 CH2=C

COOCH

2

CHCH

2 N+ C.

OH IC 3 C H =CH 2

CH

3 AN CH=CH 2

CH

2

=CI-CH

2

NH

2 C 13

CH

2

=C-CH

2

NH

2

(CH

2

=%CH-CH

2 2 NH 17 Illustrative examples of the azide-bearing amino compounds are given below.

T ~r 0 00 0 0 00 00 0 0 0 a 00 00 00 0 a 0 0 9 000

N

3 -CO CH 2

C-

2 N (CH 3 2

N

3

SO

2 c-k COO0C H2 C H 2 N (CH 3 2

N

3

(C

2

N

3 H)2 N 2) 2. C 2 CH 2 2 O H

N

3 S0 2 11 1 C N N( CH 2 2 at t C H 3

N

3

NH

N

3

SO

2 T_ -~-II 18 Particularly preferred are those compounds having a highly basic amino group represented by the formula: X 0 0-COYNR R

R

6 wherein X is -N 3 or -S0 2

N

3 Y is an alkylene group, and R4, and R6 are independently hydrogen or alkyl groups having up to 5 carbon atoms.

Solvent may be selected from those solvents in which organic pigments are insoluble, but photosensitive polyimide polymer precursors are soluble. For solubility of .o the polymer, the solvent is desirably a solvent system 00o 0 containing at least 50%, preferably at least 70% of a polar oo .15 solvent. By the polar solvent is meant a solvent having a O 0 o, solubility parameter 6 of at least 9.5. Examples of the polar solvent include dimethyl sulfoxide, dimethylformamide, 0o o dimethylacetamide, N-methyl-2-pyrrolidone, hexamethyl- O 0 phosphoroamide, and mixtures thereof.

0o0"0 Organic pigments are those pigments which have an o000o ability to color in either of the three primary colors of o light, red green and blue and which are So" sufficiently heat resistant to be applied on a substrate and heat treated at 300'C for 10 minutes without degradation, foaming or significant discoloration. The pigments o""o preferably have a particle size of up to 1 micron.

00 0 Examples of the organic pigments are well known, including quinacridone pigments as typified by Color Index No. 73905 Pigment Red 209 and 46500 Pigment Violet 19 for R (red), phthalocyanine pigments as typified by Color Index No.

74160 Pigment Green 36 and 74260 Pigment Green 7 for G (green), and Phthalocyanine Blue pigments as typified by Color Index No. 74160 Pigment Blue 15-3 and Color Index No.

74160 Pigment Blue 15-4 for B (blue).

The thus obtained photosensitive color pastes for use in coating the color filter are sufficiently heat resistant to withstand a heat treatment at 300'C or higher, preferably at 350'C for 90 minutes or more. These pastes are described in detail in Japanese Patent Application Kokai No. 61-245906, which is incorporated herein by reference.

Also, a thermosetting ink composition for color filters may be screen printed and then thermoset to form a pattern.

The thermosetting ink compositions for color filters LO are preferably those compositions comprising an epoxy resin, an organic pigment such as Phthalocyanine Blue, and a curing agent such as novolak phenol resin.

The color filters of the present invention find applications as filters in optical instruments, on cathode 15 ray tubes of outdoor displays, and on a front panel of liquid crystal TV with the advantages of weathering and chemical resistance and high transparency. They may also find utility in other applications.

1 04 0 o 0 0 90 00 00 4 o Examples 04 I O10 Examples are given below to further illustrate the a 09 present invention.

0 4 1 Example 1 A solution of 0.5 parts of maleic anhydride and o" parts of diisopropyl peroxydicarbonate in 100 parts of diethylene glycol bisallyl carbonate was cast into a casting mold composed of a glazing and a gasket of flexible polyvinyl chloride and heated in an air oven stepwise from 50'C to over 8 hours. Thereafter, the cured resin plate was taken out of the mold and fJrther heat treated at 120'C for one hour, obtaining a transparent resin plate of 2 mm thick.

The transparent resin plate was screen printed with a thermosetting ink composition for color filters which was prepared by adding 65 parts of powder Phthalocyanine Blue as ir. jr...i- NE1

I"

20 4 cc ir of a t a 04 C 0 fo 4 0.

the organic pigment to 100 parts of an epoxy resin having a number average molecular weight of 2,000 and an epoxy equivalent of 450, milling the mixture in a three-roll mill, adding 50 parts of a novolak phenol resin as the curing agent to the mixture, followed by thorough milling. The coating was heat treated at 120°C for 2 hours, obtaining a blue filter having a pattern of 2 mm squares arranged at intervals of 1 mm.

The ink topcoat on the color filter was examined for adhesion by a cross-hatched adhesion test (which is set forth in Japanese Industrial Standard -5400 as involving cutting grooves in the printed coating, applying an adhesive tape of 24 mm wide designated Nichiban Cello-Tape, and pulling off the tape at an angle of with satisfactory results.

Example 2

I

SA solution of 0.5 parts of maleic anhydride and 4 4 parts of diisopropyl peroxdicarbonate in 100 parts of liquid S composition (A)-II described later was cast into a casting mold composed of a glazing and a gasket if flexible polyvinyl chloride and heated in an air oven stepwise from 50° to over 3 hours. Thereafter, the cured resin plate was taken out of the mold and further heat treated at 120°C for one hour, obtaining a transparent resin plate of 2 mm thick.

The transparent resin plate was screen printed with a thermosetting ink composition for color filters which was prepared by adding 65 parts of powder Phthalocyanine Blue as the organic pigment to 100 parts of an epoxy resin having a number average molecular weight of 2,000 and an epoxy Sequivalent of 450, milling the mixture in a three-roll mill, jbspe.003/mitsu 91 1 7 adding 50 parts of a novolak phenol resin as the curing agent to the mixture, followed by thorough milling. The coating was heat treated at 120'C for 2 hours, obtaining a blue filter having a pattern of 2 mm squares arranged at intervals of I

MM.

4 4 S1 jbp.0/is 91 1 I

A°

21 The ink topcoat on the color filter was examined for adhesion by a cross-hatched adhesion test as in Example 1, with satisfactory results.

Example 3 A solution of 1.0 parts of maleic anhydride and parts of diisopropyl peroxydicarbonate in 100 parts of liquid composition described later was cast into a casting mold composed of a glazing and a gasket of flexible polyvinyl chloride and heated in an air oven stepwise from 50'C to over 3 hours. Thereafter, the cured resin plate was taken a, o out of the mold and further heat treated at 120'C for one hour, obtaining a transparent resin plate of 2 mm thick.

0O The transparent resin plate was screen printed with a Sthermosetting ink composition for color filters which was 0 0 o 0" 15 prepared by adding 65 parts of powder Phthalocyanine Green as o" the organic pigment to 100 parts of an epoxy resin having a o number average molecular weight of 2,000 and an epoxy 0 o equivalent of 450, milling the mixture in a three-roll mill, "o adding 50 parts of a novolak phenol resin as the curing agent oo 10 to the mixture, followed by thorough milling. The coating 0 was heat treated at 120'C for 2 hours, obtaining a blue Co filter having a pattern of 2 mm squares arranged at intervals of 1 mm.

o The ink topcoat on the color filter was examined for o 0 Z5 adhesion by a cross-hatched adhesion test as in Example 1, with satisfactory results.

Example 4 A solution of 3.0 parts of diisopropyl peroxydicarbonate in 100 parts of liquid composition (A)-II described later was cast into a casting mold composed of a glazing and a gasket of flexible polyvinyl chloride and heated in an air oven stepwise from 50'C to 85'C over 3 hours. Thereafter, the cured resin plate was taken out of i, i 22 the mold and further heat treated at 120'C for one hour, obtaining a transparent resin plate of 2 mm thick. The plate was treated with a corona discharge to adjust the surface wet tension to 52 dyne/cm.

The transparent resin plate was screen printed with a thermosetting ink composition for color filters which was prepared by adding 65 parts of powder Phthalocyanine Green as the organic pigment to 100 parts of an epoxy resin having a number average molecular weight of 2,000 and an epoxy equivalent of 450, milling the mixture in a three-roll mill, adding 50 parts of a novolak phenol resin as the curing agent.

0 e So to the mixture, followed by thorough milling. The coating 000 S was heat treated at 120'C for 2 hours, obtaining a green o oo filter having a pattern of 2 mm squares arranged at intervals 00 0 0 0 15 of 1 mm.

oo The ink topcoat on the color filter was examined for 0 0 0 o..o adhesion by a cross-hatched adhesion test as in Example 1, 00 00 °o °g with satisfactory results.

0 0 ooo0 The thus obtained color filters of Examples and 0 0 00 04 0o Q Comparative Example were subjected to the following tests.

The results are shown in Table 1.

0 o Weatherability Accelerated weathering tester (Model WEL-6X-HC-BEC, a manufactured by Suga Tester K.K.) o°S 5 Light source: 6.0 kW xenon lamp Black panel temperature: 63'C Exposure cycles each having a time of 200 minutes (including 18 minutes raining) were repeated to a total exposure time of 100 hours.

0o In the weathering test, the filters was measured for light transmittance before and after the accelerated weathering test.

i

*A

23 The liquid compositions used in Examples have the following formulation.

Composition (A)-I The reaction product obtained by reacting diallyl carbonate with diethylene glycol in a molar ratio of 2:1 in the presence of sodium ethoxide under the conditions described in Japanese Patent Application Kokai No. 56-133246 (consisting of 30% by weight of diethylene glycol bisallyl carbonate and 70% by weight it of oligo-carbonate, n 3 to 10) 55% by weight Tris(allyl carbonate) of tris(hydroxyethyl) isoo o cyanurate obtained by reacting dially carbonate with Stris(hydroxyethyl) isocyanurate in a molar ratio of o o 12:1 12.4% by weight o'dS Diethylene glycol bisallyl carbonate O A °w 27.5% by weight o Vinyl acetate 5% by weight 00 0, 0 0o o o 0 Composition (A)-IT o The reaction product obtained by reacting diallyl o 2 carbonate with diethylene glycol in a molar ratio of o 2:1 in the presence of sodium ethoxide under the oo0'0 conditions described in Japanese Patent Application Kokai No. 56-133246 (consisting of 70% by weight of diethylene glycol bisallyl carbonate and 30% by weight as of oligo-carbonate, n 3 to 10) 58% by weight Tris(allyl carbonate) of tris(hydroxyethyl) isocyanurate obtained by reacting diallyl carbonate with tris(hydroxyethyl) isocyanurate in a molar ratio of 12:1 13% by weight Diethylene glycol bisallyl carbonate 29% by weight Since the transparent substrate has improved heat, chemical and weathering resistance as well as high light i 24 transmittance, the color filter of the present invention inherits the same characteristics and exhibits excellent adhesion to printing ink.

S *0 9 6 4

I

w r Dityla glco bialy cabnt px ei o9%- a 62 maei anyrd Phhlcynn Blu seaato 90 3 a Examplehdrd Ptalcann Color seilater Constuctio 8nk Weteaity Traspaentsubtrae olor pedo laei Adeinfsbsrt DiCothyiten W-clbiallcabnt Epoxy resin No 92 2% a 620no maleic anhydride Phthalocyanlne Blue separation 9O%-*83% a 4Onm Novolak phenol resin 2 Composition (A)-lI Epoxy resin No 92%6492% a 620nm aecanyrd Phthalocyanlne Blee separation 83% a 4Onm Coroa d~chage reatentNovolak phenol resin Th laims fnhyrid phhaorann Blu sepraio disclosur af thsneiictin

Claims (7)

1. A color filter comprising a transparent substrate and a colored coating or a layer disposed on said transparent substrate, 0 t# o 0 4 l 0 0~ 0; 00 0 0( 0 3' 00 said transparent substrate comprising a polymer of a polymerizable liquid composition containing a monomer or an oligomer or a mixture thereof containing a diallyl compound as an essential component, having a general formula: f, CH

2 =CH-CH 2 -CH 2 -CH=CH 2 wherein R is a residue of a dihydric alcohol, and n has a value of an average value in the range of from 1 to 10, and aoo.. said transparent substrate being imparted with an *a00 affirity for the colored coating or layer. S 2. The color filter according to claim 1 wherein said affinity for the colored coating or layer is imparted by at 0 least one treatment selected from corona discharge, chromate and burning treatments.

3. The color filter according to claim 1 wherein said affinity for the colored coating or layer is imparted by copolymerizing said polymerizable liquid composition with an unsaturated carboxylic acid and/or its anhydride.

4. A color filter substantially as hereinbefore described with reference to figure 1 of the accompanying drawings.

A color filter substantially as hereinbefore described 25 with reference to figure 2 of the accompanying drawings. i Sjbspe.003/mitsu i jbspe. 003/mitsu 91 1 7 1"- 27

6. A color filter substantially as hereinbefore described with reference to figure 3 of the accompanying drawings.

7 January 1991 SMITH SHELSTON BEADLE Fellows Institute of Patent Attorneys of Australia Patent Attorneys for the Applicant: MITSUI PETROCHDEMICAL INDUSTRIES LTD. 0 0* 00 a Ila 0 04 00 a 00 0 a a0 a 4 4 04 1 jbspe .003/mitsu 91 1 7