TWI778035B - Negative white photosensitive resin composition and application thereof - Google Patents

Abstract

The present invention relates to a negative white photosensitive resin composition and an application thereof. The aforementioned negative white photosensitive reisn composition includes a polysiloxane (A), a compound having an ethylenically unsaturated group (B), a photo-initiator (C), a solvent (D), a white pigment (E) and a potential antioxidant (F). The negative white photosensitive resin composition has excellent sensitivity and heat-yellowing resistance.

Description

Negative white photosensitive resin composition and its application

The present invention relates to a negative-type white photosensitive resin composition and its application, in particular to provide a negative-type white photosensitive resin composition with good sensitivity and thermal yellowing resistance and its application.

In recent years, with the vigorous development of various Flat Panel Display (FPD) technologies, liquid crystal displays are widely used in various applications due to their thinning and miniaturization features. However, after a user watches the transmissive liquid crystal display with a backlight for a long time, the eyes are prone to fatigue and injury. In addition, the optical properties of the liquid crystal display often change with the change of the viewing angle. In order to improve this problem, the industry has developed a reflective display device, which is thinner than a liquid crystal display, saves power, and puts less burden on the eyes of users.

A reflective display device is a display that displays an image by reflecting the incident light from the external environment, and a specific example thereof is a reflective liquid crystal display or an electronic paper display.

E-paper display is a new type of display technology that can convert text on paper. The above-mentioned "paper" is actually made of organic electronic materials, and uses microspheres that can be affected by an electric field to display images. The pixel transformation method of the electronic paper display is similar to the transformation method of the personal computer display, and the page is updated through the pixel transformation.

There are roughly two ways to obtain color display images in today's color electronic paper displays; one is to use color (RGB/CYM) particles instead of white particles; the other is to set color filters on the electronic paper display to achieve color display. show.

Rigid electronic paper displays can directly manufacture color filters on glass substrates, but the cost is expensive, and the glass substrate and the color filters on the electronic paper display elements need to be aligned and assembled, which also increases the difficulty of manufacturing. In addition, flexible electronic paper displays cannot use the above scheme to make color filters at all.

Another low-cost method is to directly form the pixel pattern of the color filter on the display layer of the electronic paper. As described in Japanese Patent Laid-Open No. 2009-531727, this color filter uses a photosensitive resin composition to form a pixel pattern, and the material used for the light shielding portion is a white resin composition. However, for a reflective display device that uses an ambient light source to display images, the light transmittance and light utilization rate are reduced, and the brightness is not good.

In order to improve the aforementioned problems, Japanese Patent Laid-Open No. 2008-129599 discloses that the use of a white resin composition as a light shielding portion can improve the light utilization rate, but has the problem of poor sensitivity and thermal yellowing resistance.

On the other hand, flat panel displays have been widely combined with touch panels in recent years, and are used in consumer electronic products such as mobile devices, digital cameras, and satellite navigators. When assembling the flat panel display and the touch panel, a frame is usually set to shield the circuits around the touch panel. However, current borders are mostly black or silver, thus limiting product color and variability. To give the product a better appearance, use a white resin composition to form a white border. However, the commonly used white resin compositions have problems of poor sensitivity and thermal yellowing in the manufacturing process.

Therefore, how to provide a white photosensitive resin composition with good sensitivity and thermal yellowing resistance is a problem that those skilled in the art are eager to solve.

Therefore, one aspect of the present invention is to provide a negative-type white photosensitive resin composition. The negative-type white photosensitive resin composition comprises polysiloxane (A), compound (B) having ethylenically unsaturated group, photoinitiator (C), solvent (D), white pigment (E) and latent Antioxidant (F), and the negative-type white photosensitive resin composition has good sensitivity and heat-resistant yellowing.

Another aspect of the present invention is to provide a white matrix formed by the aforementioned negative-type white photosensitive resin composition.

Another aspect of the present invention is to provide a color filter comprising the aforementioned white matrix.

Another aspect of the present invention is to provide a reflective display device including the aforementioned color filter.

Yet another aspect of the present invention is to provide a white frame formed from the aforementioned negative-type white photosensitive resin composition.

Yet another aspect of the present invention is to provide a display device including the aforementioned white frame.

According to the above aspect of the present invention, a negative-type white photosensitive resin composition is proposed. The negative-type white photosensitive resin composition may comprise polysiloxane (A), compound (B) having ethylenically unsaturated group, photoinitiator (C), solvent (D), white pigment (E) and The latent antioxidant (F) is described below.

Polysiloxane (A)

The type of the polysiloxane (A) of the present invention is not particularly limited as long as the object of the present invention can be achieved. The polysiloxane (A) of the present invention can be obtained by performing a polycondensation reaction (ie, performing a hydrolysis reaction and a partial condensation reaction) with a mixture comprising a silane monomer, or a silane monomer and other polymerizable compounds.

The silane monomer may include silane monomer (a-1) and silane monomer (a-2).

Silane monomer (a-1)

The silane monomer (a-1) is a compound represented by the following formula (III-1): Si(R ₁ ) _w (OR ₂ ) _4-w (III-1)

In formula (III-1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons, an aryl group having 6 to 15 carbons, an acid anhydride alkyl group having 1 to 10 carbon atoms, alkyl group having epoxy group and carbon number 1 to 10, or alkoxy group having epoxy group, wherein at least one R ₁ represents an acid anhydride group and carbon number 1 an alkyl group having to 10, an alkyl group having an epoxy group and a carbon number of 1 to 10, or an alkoxy group having an epoxy group; R ₂ independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 6, a carbon an acyl group having a number of 1 to 6 or an aryl group having a carbon number of 6 to 15; and w represents an integer of 1 to 3.

When R ₁ of the aforementioned formula (III-1) represents an alkyl group having 1 to 10 carbon atoms, R ₁ may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl , n-hexyl or n-decyl. Secondly, this R ₁ can also be an alkyl group with other substituents, specifically, R ₁ can be, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercapto propyl or 3-isocyanatopropyl.

When R ₁ in the aforementioned formula (III-1) represents an alkenyl group having a carbon number of 2 to 10, R ₁ may be, for example, a vinyl group. Secondly, R ₁ may also be an alkenyl group having other substituents, and specifically, R ₁ may be, for example, 3-acryloyloxypropyl or 3-methacryloyloxypropyl.

When R ₁ of the aforementioned formula (III-1) represents an aromatic group having a carbon number of 6 to 15, R ₁ may be, for example, phenyl, tolyl, or naphthyl. Secondly, R ₁ may also be an aryl group having other substituents, specifically, R ₁ is, for example, p-hydroxyphenyl (p-hydroxyphenyl), 1-(p-hydroxyphenyl) ethyl [1-(p -hydroxyphenyl)ethyl], 2-(p-hydroxyphenyl)ethyl[2-(p-hydroxyphenyl)ethyl] or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl[4-hydroxy -5-(p-hydroxyphenylcarbonyloxy)pentyl].

When R ₁ of the aforementioned formula (III-1) represents an alkyl group having an acid anhydride group and a carbon number of 1 to 10, R ₁ can be, for example, ethyl succinic anhydride represented by the following formula (III-1-1), propyl succinic anhydride represented by formula (III-1-2) or propyl glutaric anhydride represented by formula (III-1-3). Wherein, the acid anhydride group is a group formed by intramolecular dehydration of dicarboxylic acid, wherein the dicarboxylic acid can be, for example, succinic acid or glutaric acid:

When R ₁ of the aforementioned formula (III-1) represents an alkyl group having an epoxy group and a carbon number of 1 to 10, R ₁ may be, for example, oxetanylpentyl or 2-(3,4- Epoxycyclohexyl)ethyl[2-(3,4-epoxycyclohexyl)ethyl]. Second, the epoxy group may be a group formed by intramolecular dehydration of a diol, wherein the diol may be, for example, propylene glycol, butanediol, or pentanediol.

When R ₁ of the aforementioned formula (III-1) represents an alkoxy group having an epoxy group, R ₁ may be, for example, glycidoxypropyl or 2-glycidoxypropyl (2-glycidoxypropyl) oxetanylbutoxy).

When R ₂ in the aforementioned formula (III-1) represents an alkyl group having a carbon number of 1 to 6, R ₂ may be, for example, methyl, ethyl, n-propyl, isopropyl or n-butyl. When R ₂ in the formula (III-1) represents an acyl group having a carbon number of 1 to 6, R ₂ may be, for example, an acetyl group. When R ₂ in formula (III-1) represents an aromatic group having a carbon number of 6 to 15, R ₂ may be, for example, a phenyl group.

In formula (III-1), w represents an integer of 1 to 3. When w represents 2 or 3, R ₁ in the multiple repeating units may be the same or different; when w represents 1 or 2, R ₂ in the multiple repeating units may be the same or different.

Specific examples of the silane monomer represented by formula (III-1) include but are not limited to 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane; TMS-GAA), 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane 2-oxetanylbutoxypropyl triphenoxysilane; the following commercially available products manufactured by Toagosei: 2-oxetanylbutoxypropyltrimethoxysilane (2-oxetanylbutoxypropyltrimethoxysilane) ; and its trade name is TMSOX-D), 2-oxetanylbutoxypropyltriethoxysilane (and its trade name is TESOX-D) or 3-(triphenoxysilane) propyl) propyl succinic anhydride, etc.; the following commercially available products manufactured by Shin-Etsu Chemical: 3-(trimethoxysilyl) propyl succinic anhydride (its trade name is X-12-967); manufactured by WACKER Corporation Manufactured the following commercial products: 3-(triethoxysilyl)propylsuccinic anhydride (its trade name is GF-20); 3-(trimethoxysilyl)propylglutaric anhydride (abbreviated as TMSG) ), 3-(triethoxysilyl)propylglutaric anhydride or 3-(triphenoxysilyl)propylglutaric anhydride, etc.; Oxypropyl) silane [diisopropoxy-di(2-oxetanylbutoxypropyl)silane; DIDOS], bis(3-epoxypropylpentyl)dimethoxysilane [di(3-oxetanylpentyl)dimethoxy silane], (di-n-butoxysilyl)bis(propyl succinic anhydride), (dimethoxysilyl)bis(ethylsuccinic anhydride), 3-epoxy 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, bis(2-glycidoxypropyldimethylethoxysilane) Pentyl)-2-oxiranylpentylethoxysilane [di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxysilane], tris(2-oxiranylpentyl)methoxysilane [tri(2 -oxetanylpentyl)methoxy silane], (phenoxysilyl)tris(propylsuccinic anhydride), (methylmethoxysilyl)bis(ethylsuccinic anhydride), other suitable silane monomers or the above compounds any combination of . The aforementioned silane monomers may be used alone or in combination.

Preferably, specific examples of the silane monomer represented by formula (III-1) may include 3-(triethoxysilyl)propylsuccinic anhydride, 3-(trimethoxysilyl)propylpentane Dianhydride, (dimethoxysilyl)bis(ethylsuccinic anhydride), 2-epoxypropenylbutoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 2-glycidylbutoxypropyltriethoxysilane, or any combination of the above.

Based on the total usage amount of the silane monomer being 100 mole percent, the usage amount of the silane monomer represented by formula (III-1) may be 1 mole percent to 6 mole percent, preferably 2 mole percent to 6 mole percent, and more preferably 2 mole percent to 5 mole percent.

If the silane monomer contains the silane monomer represented by formula (III-1), the prepared negative-type white photosensitive resin composition has better thermal yellowing resistance.

Silane monomer (a-2)

The silane monomer (a-2) can be a silane monomer represented by the following formula (III-2): Si(R ₃ ) _e (OR ₄ ) _4-e (III-2)

In formula (III-2), R ₃ independently represents a hydrogen atom, an alkyl group with a carbon number of 1 to 10, an alkenyl group with a carbon number of 2 to 10 or an aryl group with a carbon number of 6 to 15; R ₄ respectively independently represents a hydrogen atom, an alkyl group having 1 to 6 carbons, an acyl group having 1 to 6 carbons, or an aryl group having 6 to 15 carbons; and e represents an integer of 0 to 3.

When R ₃ in formula (III-2) represents an alkyl group having a carbon number of 1 to 10, R ₃ may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl , n-hexyl or n-decyl. Secondly, R ₃ can also be an alkyl group with other substituents, specifically, R ₃ can be, for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl group or 3-isocyanatopropyl.

When R ₃ in formula (III-2) represents an alkenyl group having a carbon number of 2 to 10, R ₃ may be, for example, a vinyl group. Secondly, R ₃ may also be an alkenyl group having other substituents, and specifically, R ₃ may be, for example, 3-acryloyloxypropyl or 3-methacryloyloxypropyl.

When R ₃ in formula (III-2) represents an aromatic group having a carbon number of 6 to 15, R ₃ may be, for example, phenyl, tolyl, or naphthyl. Secondly, R ₃ can be an aryl group with other substituents, specifically, R ₃ can be, for example, p-hydroxyphenyl (p-hydroxyphenyl), 1-(p-hydroxyphenyl) ethyl [1-(p -hydroxyphenyl)ethyl], 2-(p-hydroxyphenyl)ethyl[2-(p-hydroxyphenyl)ethyl] or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl[4-hydroxy -5-(p-hydroxyphenylcarbonyloxy)pentyl].

When R ₄ of formula (III-2) represents an alkyl group having a carbon number of 1 to 6, R ₄ may be, for example, methyl, ethyl, n-propyl, isopropyl or n-butyl. When R ₄ in the formula (III-2) represents an acetyl group having a carbon number of 1 to 6, specifically, R ₄ may be, for example, an acetyl group. When R ₄ in formula (III-2) represents an aromatic group having a carbon number of 6 to 15, R ₄ may be, for example, a phenyl group.

In formula (III-2), e is an integer of 0 to 3. When e represents 2 or 3, R ₃ in the multiple repeating units can be the same or different; when e represents 0, 1 or 2, R ₄ in the multiple repeating units can be the same or different.

In formula (III-2), when e=0, the silane monomer of formula (III-2) is a tetrafunctional silane monomer (that is, a silane monomer with four hydrolyzable groups); when e When e=1, the silane monomer of formula (III-2) is a trifunctional silane monomer (that is, a silane monomer with three hydrolyzable groups); when e=2, the silane monomer of formula (III-2) The silane monomer is a difunctional silane monomer (that is, a silane monomer having two hydrolyzable groups); and when e=3, the silane monomer of formula (III-2) is a monofunctional silane monomer (ie silane monomers with one hydrolyzable group). It is worth mentioning that the hydrolyzable group refers to a group that can undergo hydrolysis reaction and bond with silicon, for example, the hydrolyzable group can be, for example, an alkoxy group, an acyloxy group or phenoxy group.

Specific examples of the silane monomer represented by the aforementioned formula (III-2) may include but are not limited to: (1) Tetrafunctional silane monomer: such as tetramethoxysilane (tetramethoxysilane), tetraethoxysilane, tetraacetoxysilane, or tetraphenoxy silane, etc.; (2) Trifunctional silane monomer: such as methyltrimethoxysilane Silane (methyltrimethoxysilane; MTMS), methyltriethoxysilane (methyltriethoxysilane), methyltriisopropoxysilane (methyltriisopropoxysilane), methyltri-n-butoxysilane (methyltri-n-butoxysilane), ethyltrimethoxysilane Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyl n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Silane (vinyltriethoxysilane), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane (p-hydroxyphenyltrimethoxy), 1-(p- Hydroxyphenyl)ethyltrimethoxysilane[1-(p-hydroxyphenyl)ethyltrimethoxysilane], 2-(p-hydroxyphenyl)ethyltrimethoxysilane Methoxysilane [2-(p-hydroxyphenyl)ethyltrimethoxysilane], 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane [4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl] trimethoxysilane], trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane (3,3,3-trifluoropropyltrimethoxysilane) ), 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propenyloxypropyl (3) Difunctional silane monomers: such as di- Methyldimethoxysilane (dimethyldimethoxysilane; DMDMS), dimethyldiethoxysilane (dimethyldiethoxysilane), dimethyldiacetyloxysilane (dimethyldiacetyloxysilane), di-n-butyldimethoxysilane (di- n-butyldimethoxysilane) or diphenyldimethoxysilane, etc.; or (4) Monofunctional silane monomers: such as trimethylmethoxysilane or tri-n-butylethoxysilane ( tri-n-butylethoxysilane) and so on.

The silane monomer represented by the aforementioned formula (III-2) may be used alone or in combination of two or more.

Based on the total usage amount of silane monomer being 100 mole percent, the usage amount of the silane monomer represented by formula (III-2) may be 94 mole percent to 99 mole percent, preferably 94 mole percent to 98 mole percent, and more preferably 95 mole percent to 98 mole percent.

The aforementioned other polymerizable compounds may comprise siloxane prepolymers, silica particles, or any combination of the foregoing materials.

The siloxane prepolymer may comprise a compound represented by the following formula (III-3):

In formula (III-3), R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number of The aryl group of 6 to 15, wherein any one of the alkyl group, alkenyl group and aryl group can optionally contain a substituent; R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 6, The aryl group having 1 to 6 carbon atoms or the aryl group having 6 to 15 carbon atoms, wherein any one of the alkyl group, the aryl group and the aryl group may optionally contain a substituent; and f represents an integer of 1 to 1000.

In more detail, when R ₅ , R ₆ , R ₇ and R ₈ in formula (III-3) each independently represent an alkyl group having 1 to 10 carbon atoms, R ₅ , R ₆ , R ₇ and R ₈ For example, each independently may represent methyl, ethyl or n-propyl. When R ₅ , R ₆ , R ₇ and R ₈ in formula (III-3) each independently represent an alkenyl group having 2 to 10 carbon atoms, for example, R ₅ , R ₆ , R ₇ and R ₈ each independently stands for vinyl, acryloxypropyl or methacryloyloxypropyl. When R ₅ , R ₆ , R ₇ and R ₈ in formula (III-3) each independently represent an aromatic group having 6 to 15 carbon atoms, for example, R ₅ , R ₆ , R ₇ and R ₈ each independently represent Phenyl, tolyl or naphthyl. Here, any one of the alkyl group, the alkenyl group, and the aryl group may have other substituents.

Next, when R ₉ and R ₁₀ of formula (III-3) each independently represent an alkyl group having 1 to 6 carbon atoms, R ₉ and R ₁₀ each independently represent, for example, methyl, ethyl, n-propyl, isopropyl propyl or n-butyl. When R ₉ and R ₁₀ of formula (III-3) each independently represent an acetyl group having a carbon number of 1 to 6, R ₉ and R ₁₀ may be, for example, an acetyl group. When R ₉ and R ₁₀ in formula (III-3) each independently represent an aromatic group having a carbon number of 6 to 15, R ₉ and R ₁₀ may be, for example, a phenyl group. Here, any one of the above-mentioned alkyl group, acyl group, and aryl group may optionally have a substituent.

In formula (III-3), f may be an integer of 1 to 1000, preferably an integer of 3 to 300, and more preferably an integer of 5 to 200. Wherein, when f is an integer from 2 to 1000, each of R ₅ in the plurality of repeating units is the same or different group, and each of R ₆ in the plurality of repeating units is the same or different group.

Specific examples of the aforementioned siloxane prepolymer represented by formula (III-3) may include, but are not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-Tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane, Or Silanol-terminated polydimethylsiloxane (Silanol-terminated polydimethylsiloxane) manufactured by Gelest Company and having a silanol-terminated group is commercially available. (molecular weight is 1500 to 2000), DMS-S21 (molecular weight is 4200), DMS-S27 (molecular weight is 18000), DMS-S31 (molecular weight is 26000), DMS-S32 (molecular weight is 36000), DMS-S33 (molecular weight is 36000) 43500), DMS-S35 (molecular weight is 49000), DMS-S38 (molecular weight is 58000), DMS-S42 (molecular weight is 77000) or PDS-9931 (molecular weight is 1000 to 1400), etc.

The aforementioned siloxane prepolymers may be used alone or in combination.

The average particle size of the silica particles is not particularly limited. And the average particle size can range from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more preferably from 10 nm to 100 nm.

Specific examples of the silica particles include, but are not limited to, commercially available products manufactured by Catalyst Chemicals, and their trade names may be, for example, OSCAR 1132 (particle size is 12 nm, and dispersant is methanol), OSCAR 1332 (12 nm particle size and n-propanol as dispersant), OSCAR 105 (60 nm particle size and γ-butyrolactone as dispersant) or OSCAR 106 (120 nm particle size and diacetone alcohol as dispersant) etc.; commercially available products manufactured by Fuso Chemical Company, and the trade names may be, for example, Quartron PL-1-IPA (particle size is 13 nm, and dispersant is isoacetone), Quartron PL-1-TOL (particle size is 13 nm) , and the dispersing agent is toluene), Quartron PL-2L-PGME (the particle size is 18 nm, and the dispersing agent is propylene glycol monomethyl ether) or Quartron PL-2L-MEK (the particle size is 18 nm, and the dispersing agent is methyl ethyl ketone), etc.; Or a commercial product manufactured by Nissan Chemical Co., Ltd., and the trade name can be, for example, IPA-ST (particle size is 12 nm, and the dispersing agent is isopropanol), EG-ST (particle size is 12 nm, and the dispersing agent is ethyl alcohol). diol), IPA-ST-L (45 nm particle size and isopropanol as dispersant) or IPA-ST-ZL (100 nm particle size and isopropanol as dispersant). The aforementioned silica particles may be used alone or in combination of a plurality of them.

Synthesis method of polysiloxane (A)

The polysiloxane (A) can be formed by performing a polycondensation reaction using the aforementioned silane monomer, or by performing a polycondensation reaction using a silane monomer and other polymerizable compounds. Generally speaking, the above-mentioned polycondensation reaction is carried out by the following steps: adding a solvent, water, and optionally a catalyst to the silane monomer; and heating and stirring at 50° C. to 150° C. for 0.5 hours to 120 hours, and further by-products (such as alcohols, water, etc.) can be removed by distillation.

The solvent used for the polycondensation reaction is not particularly limited, and the solvent may be the same as or different from the solvent (D) included in the photosensitive resin composition of the present invention. The solvent may be used in an amount of 20 grams to 1000 grams, preferably 30 grams to 800 grams, and more preferably 50 grams to 600 grams, based on 1 mole of the total amount of silane monomer used.

Based on the hydrolyzable group of the silane monomer being 1 mole, the water used in the polycondensation reaction (that is, the water used for hydrolysis) may be 5 g to 500 g, preferably 10 g to 400 g, and more preferably 15 grams to 300 grams.

The catalyst used in the polycondensation reaction is not particularly limited, and may preferably be selected from acid catalysts or alkali catalysts. Specific examples of the acid catalyst may include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, or ion exchange resin. Specific examples of alkali catalysts may include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, hydroxide Sodium, potassium hydroxide, silane containing amine group and alkoxy group, or ion exchange resin, etc.

Based on the total usage amount of the silane monomer being 1 mole, the usage amount of the catalyst may be 0.05 grams to 5 grams, preferably 0.07 grams to 4 grams, and more preferably 0.1 grams to 3 grams.

From the viewpoint of stability, the polysiloxane (A) preferably does not have by-products (such as alcohols or water) and catalysts. Therefore, the polysiloxane (A) can be obtained by selectively purifying the reaction mixture after the polycondensation reaction. The method of purification is not particularly limited, and preferably the reaction mixture can be diluted with a hydrophobic solvent. Next, the hydrophobic solvent and reaction mixture were transferred to a separation funnel. Then, the organic layer was washed several times with water, and the organic layer was concentrated with a rotary evaporator to remove alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.

The polysiloxane (A) may be used in combination with other alkali-soluble resins. The kinds of the other alkali-soluble resins are not particularly limited, and they may include, but are not limited to, resins containing carboxylic acid groups or hydroxyl groups. Specific examples of other alkali-soluble resins may include acrylic resins, fluorene resins, urethane resins, or novolac resins.

Compound (B) having ethylenically unsaturated group

The compound (B) having an ethylenically unsaturated group of the present invention may include a compound having one ethylenically unsaturated group, a compound having two or more ethylenically unsaturated groups, or any combination of the above-mentioned compounds.

Specific examples of the aforementioned compound having one ethylenically unsaturated group may include but are not limited to (meth)acrylamide [(meth)acrylamide], (meth)acrylmorpholine], (meth)acrylmorpholine ) propylene Acid-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate ester, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, tertiary octyl (meth)acrylamide, diacetone (meth)acrylamide, Dimethylaminoethyl (meth)acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N , N-dimethyl(meth)acrylamide, tetrachlorophenyl(meth)acrylate, 2-tetrachlorophenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate[ tetrahydrofurfuryl(meth)acrylate], tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, ( Tribromophenyl meth)acrylate, 2-Tribromophenoxyethyl (meth)acrylate, Ethyl 2-hydroxy-(meth)acrylate, Propyl 2-hydroxy-(meth)acrylate, Ethylene Ethyl caprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polymono(meth)acrylic acid Ethylene glycol, polypropylene mono(meth)acrylate, bornyl (meth)acrylate, or any combination of the above. The aforementioned compound having one ethylenically unsaturated group may be used alone or in combination of two or more.

Specific examples of the aforementioned compound having two or more ethylenically unsaturated groups may include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate base) acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl) isocyanate di(meth)acrylate, tris(2-hydroxyethyl) isocyanate tri(meth)acrylate base) acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tri(methyl)propylene Trimethylolpropyl enoate, trimethylolpropyl acrylate modified with ethylene oxide (EO), trimethylolpropyl acrylate modified with propylene oxide (PO) Methylol propyl ester, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di- Pentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate Acrylates, di(trimethylolpropane)tetra(meth)acrylate, bisphenol A di(meth)acrylate modified with ethylene oxide, epoxy Propane-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide-modified hydrogenated bisphenol A di(meth)acrylate ) acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, novolac polyglycidyl ether (meth)acrylate, or any combination of the foregoing. The aforementioned compounds having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.

Based on the total usage amount of polysiloxane (A) being 100 parts by weight, the usage amount of the compound (B) having an ethylenically unsaturated group carried by the present invention may be 30 parts by weight to 200 parts by weight, preferably 35 parts by weight parts to 160 parts by weight, and more preferably 40 parts to 130 parts by weight.

Photoinitiator (C)

The photoinitiator (C) of the present invention may comprise a photoinitiator (C-1) represented by the following formula (I):

，且X₅代表

、

、

、

、

、

、

、

，其中X₅₁代表甲基或乙基，且X₅₂代表氫原子或甲基。 In formula (I), X ₁ represents -O-, -S- or -Se-; X ₂ represents a phenyl group with 1 to 5 methyl groups; X ₃ represents an alkyl group with 1 to 10 carbon atoms, benzene group, or a cycloalkyl group with a carbon number of 3 to 6; X ₄ represents a hydrogen atom or

, and X ₅ represents

,

,

,

,

,

,

,

, wherein X ₅₁ represents a methyl group or an ethyl group, and X ₅₂ represents a hydrogen atom or a methyl group.

X ₁ in formula (I) can preferably be -O- or -S-.

、

或

。 X in _formula (I) preferably can be

,

or

.

X ₃ can preferably be methyl or phenyl.

時，X₅較佳可為

或

。 When X ₄ stands for

, X ₅ is preferably

or

.

In a specific example, the photoinitiator (C-1) represented by the formula (I) may include, but is not limited to, the photoinitiators represented by the following formulas (I-1) to (I-18).

The synthesis method of the photoinitiator (C-1) represented by the formula (I) can be, for example, the following scheme I shown below.

First, in the presence of aluminum chloride, a diphenyl compound and an N-methylcarbonyl chloride compound (eg, N-trimethyl phenyl carbonyl chloride) are reacted, To obtain the acyl compound represented by formula (I'-1). Then, in the presence of a basic catalyst (eg, sodium methoxide), the acyl compound is reacted with isoamyl nitrite to obtain an α -ketoxime represented by formula (I'-2) Compound (α-ketoxime compound). Next, in the presence of a triethylamine catalyst, the α -ketoxime compound is reacted with the carboxychloride compound to obtain the α -ketoxime ester compound (α-ketoxime ester) represented by the above formula (I'-3). ).

In some embodiments, the synthesis method of the photoinitiator (C-1) represented by formula (I) can be, for example, Scheme II shown below.

First, in the presence of aluminum chloride, a diphenyl compound, a carbohydrin compound, and an N-methylcarbohydrin compound (eg, N-trimethylphenylcarbohydrin compound) are reacted to obtain a compound such as The acyl compound represented by the formula (I'-4). Then, in the presence of a basic catalyst (eg, sodium methoxide), the acyl compound is reacted with isoamyl nitrite to obtain an α -ketoxime compound (α-ketoxime) represented by formula (I'-5) ketoxime compound). Next, in the presence of a triethylamine catalyst, the α -ketoxime compound is reacted with the carboxychloride compound to obtain the α -ketoxime ester compound (α-ketoxime ester) represented by the above formula (I'-6). ).

The aforementioned photoinitiator (C-1) may be used alone or in combination of two or more.

Based on 100 parts by weight of polysiloxane (A), the amount of photoinitiator (C-1) can be 3 to 30 parts by weight, preferably 4 to 26 parts by weight, and More preferably, it is 5 to 22 parts by weight.

If the photoinitiator (C) of the present invention does not contain the photoinitiator (C-1) represented by the formula (I), the prepared negative-type white photosensitive resin composition has poor sensitivity and heat resistance yellowing.

In addition to the aforementioned photoinitiator (C-1), the photoinitiator (C) of the present invention may optionally contain other photoinitiators (C-2).

Other photoinitiators (C-2) may include, but are not limited to, Oxime-based photoinitiators, Triazine-based photoinitiators, acetophenones compound, biimidazole or benzophenone.

Specific examples of O-acyl oxime-based photoinitiators may include, but are not limited to, 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzyl oxime) {1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime)}, 1-[4-(phenylthio)phenyl]-octane-1, 2-Dione 2-(O-benzoyloxime){1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime)}, 1-[4-(benzoyloxime) base)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime){1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime )}, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime){1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethanone 1-(O-acetyloxime)}, 1-[9-ethyl-6-(3-methylbenzoyl) -9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime){1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazole-3-yl]-ethanone 1-(O-acetyloxime)}, 1-[9-ethyl-6-benzyl-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime){1-[ 9-ethyl-6-benzoyl-9H-carbazole-3-yl]-ethanone 1-(O-acetyloxime)}, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H- carbazole-3-yl]-1-(O-acetyloxime)}, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl benzoyl)-9H- Carbazol-3-yl]-1-(O-acetyloxime){ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-yl]-1 -(O-acetyloxime)}, ethanone -1-[9-Ethyl-6-(2-methyl-5-tetrahydrofuranylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime){ethanone-1 -[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)}, ethanone-1-[9-ethyl-6- (2-Methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime){ethanone-1-[9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)}, ethanone-1-[9-ethyl-6-(2-methyl-4- THF )-9H-carbazole-3-yl]-1-(O-acetyloxime)}, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxy) Benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime){ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazole -3-yl]-1-(O-acetyloxime)}, ethanone-l1[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzyl)-9H-carbazole -3-yl]-1-(O-acetyloxime){ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3-yl]-1-( O-acetyloxime)}, ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl] -1-(O-acetyloxime){ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)} , Ethanone-1-{9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolane Cyclo)benzyl]-9H-carbazol-3-yl}-1-(O-acetyloxime){ethanone-1-{9-ethyl-6-[2-methyl-4-(2, 2-dimethyl-1,3-dioxolanyl)benzoyl]-9H-carbazole-3-yl}-1-(O-acetyloxime)}, ethanone-1-{9-ethyl-6-[2-methyl] -4-(2,2-Dimethyl-1,3-dioxolanyl)methoxybenzyl]-9H-carbazol-3-yl}-1-(O-acetyloxime ){ethanone-1-{9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl]-9H-carbazole-3-yl}-1-(O- acetyloxime)}, or any combination of the above compounds.

Specific examples of triazine-based photoinitiators may include, but are not limited to, 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis( Trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloro Methyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene , 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p- -N-Chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-ethoxycarbonylmethylaminophenyl)- 2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(phenyl)aminophenyl]-2,6-bis(trichloromethyl) -s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N -(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-N,N-bis(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl) )aminophenyl]-2,6-bis(trichloromethane base)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)- s-triazabenzene, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-tri Azabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene , 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[ o-Fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo -p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N -Bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-bis(chloroethyl) )aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl] -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di (Trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl) -s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p -N-Ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethyl) aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2 ,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl) base)-s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethane) base)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4 -(m-Fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloro Ethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6 -Bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s- Triazine, 2,4-bis(trichloromethyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3 , 5-Triazabenzene, or any combination of the above compounds.

Specific examples of acetophenone compounds may include, but are not limited to, p-dimethylamino-acetophenone, α,α'-dimethoxy azo acetophenone ( α,α'-dimethoxyazoxyacetophenone), 2,2'-dimethyl-2-phenylacetophenone (2,2'-dimethyl-2-phenylacetophenone), p-methoxyacetophenone (p- methoxyacetophenone), 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propane[2-methyl-1-(4-methylthiophenyl)-2-morpholino propane-1- one], 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone[2-benzyl-2-N,N-dimethylamino-1-( 4-morpholinophenyl)-1-butanone], or any combination of the above compounds.

Specific examples of biimidazole compounds may include, but are not limited to, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole[2,2'- bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl- biimidazole], 2,2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole[2,2'-bis(o-fluorophenyl)-4,4', 5,5'-tetraphenylbiimidazole], 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole[2,2'-bis(o-methyl phenyl) )-4,4',5,5'-tetraphenylbiimidazole], 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole[2,2 '-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole], 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl Diimidazole[2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenylbiimidazole], 2,2'-bis(p-methoxyphenyl)-4,4',5 ,5'-Tetraphenylbiimidazole[2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole], 2,2'-bis(2,2',4,4 '-Tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazo[2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4' ,5,5'-tetraphenylbiimidazole], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole[2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetraphenyl biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl biimidazole[2, 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole], or any combination of the above compounds.

Specific examples of benzophenone compounds may include, but are not limited to, thioxanthone, 2,4-diethylthioxanthanone, thioxanthone-4-oxanthone ( thioxanthone-4-sulfone), benzophenone, 4,4'-bis(dimethylamino) benzophenone [4,4'-bis(dimethylamino) benzophenone], 4,4'-bis(diethylamino)benzophenone [4,4'-bis(diethylamino)benzophenone], or any combination of the above compounds.

Preferably, specific examples of other photoinitiators (C-2) may include 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime), ethane Keto-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), Ethanone-1-{9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolane)methoxybenzyl]- 9H-carbazol-3-yl}-1-(O-acetyloxime), 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2 ,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, 2- Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-tetraphenyldiimidazole, 4,4'-bis(diethylamine)benzophenone, or any combination of the above compounds.

In addition, within the range that does not affect the physical properties, the negative-type white photosensitive resin composition of the present invention can further add photoinitiators other than the aforementioned photoinitiators, for example: α-diketone (α-diketone) compounds as required. , acyloin compounds, acyloin ether compounds, acylphosphineoxide compounds, quinone compounds, halogen-containing compounds, peroxides, or any of the above compounds combination.

Specific examples of α-diketone compounds may include, but are not limited to, benzil, acetyl, etc.; specific examples of ketone alcohol compounds may include, but are not limited to, benzoin, etc.; Specific examples of ketol ether compounds may include, but are not limited to, benzoin methylether, benzoin ethylether, or benzoin isopropyl ether, etc.; phosphine Specific examples of oxide compounds may include, but are not limited to, Bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide, 2,4 , 2,4,6-trimethyl-benzoyldiphenyl phosphineoxide or bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethyl phenylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide], etc.; specific examples of quinone compounds may include but are not limited to anthraquinone or 1,4 - Naphthoquinone (1,4-naphthoquinone), etc.; specific examples of halogen-containing compounds may include, but are not limited to, phenacyl chloride, tribromomethyl phenylsulfone, or tris(trichloromethyl) [tris(trichloromethyl)-s-triazine], etc.; specific examples of peroxides may include, but are not limited to, di-tertbutylperoxide (di-tertbutylperoxide) and the like.

The aforementioned photoinitiator (C) may be used alone or in combination of two or more.

Based on the total usage amount of polysiloxane (A) being 100 parts by weight, the usage amount of the photoinitiator (C) may be 3 parts by weight to 45 parts by weight, preferably 4 parts by weight to 40 parts by weight, and More preferably, it is 5 to 35 parts by weight.

Solvent (D)

As long as the solvent (D) of the present invention can dissolve the polysiloxane (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the white pigment (E) and the latent antioxidant ( F) and a solvent that does not react with each of the above-mentioned components may be sufficient and is not particularly limited. The solvent (D) preferably has suitable volatility.

Specific examples of the solvent (D) may include, but are not limited to, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether ( (poly)alkylene glycol monoalkyl ether solvents such as tripropylene glycol mono methyl ether) or tripropylene glycol mono ethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, (poly)alkylene glycol monoalkyl ether acetate solvents such as propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate; diglyme, diglyme, diglyme or tetrahydrofuran, etc. Other ether solvents; ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or 4-hydroxy-4-methyl-2-pentanone; methyl 2-hydroxypropionate or 2- Alkyl lactate solvents such as ethyl hydroxypropionate; methyl 2-hydroxy-2-methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl 3-methoxypropionate, 3 - Ethyl methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid n-amyl, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvic acid Other ester solvents such as n-propyl ester, methyl acetoacetate, ethyl acetate or ethyl 2-oxybutyrate; aromatic hydrocarbon solvents such as toluene or xylene; N-methylpyrrolidone, Carboxylic amide solvents such as N,N-dimethylformamide or N,N-dimethylacetamide, or any combination of the above solvents. The aforementioned solvents may be used alone or in combination. Specific examples of the solvent (D) may preferably include propylene glycol ethyl ether, 4-hydroxy-4-methyl-2-pentanone, or any combination of the above solvents.

Based on the total usage amount of the polysiloxane (A) being 100 parts by weight, the usage amount of the solvent (D) may be 100 parts by weight to 700 parts by weight, preferably 120 parts by weight to 600 parts by weight, and more preferably 150 parts by weight parts by weight to 500 parts by weight.

White Pigment (E)

Specific examples of the white pigment (E) of the present invention may include at least strontium titanate (SrTiO ₃ ), titanium dioxide, calcium carbonate, calcium sulfate, zinc oxide, barium sulfate, barium carbonate, silicon dioxide, aluminum powder, kaolin, clay, Talc, montmorillonite, aluminum hydroxide, magnesium carbonate, white hollow polymer microspheres, or any combination of the above materials.

If the negative-type white photosensitive resin composition of the present invention does not use the white pigment (E), the light transmittance of the formed pattern is too high to reflect light Line, there will be the problem of poor reflectivity, and too high light transmittance is easy to cause defects that cannot shield the light.

The aforementioned white pigments (E) may be used alone or in combination of two or more.

The white pigment (E) of the present invention may optionally be accompanied by a dispersant if necessary. The dispersing agent may include, but is not limited to, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane-based surfactants, fluorine-based surfactants, or the above interfaces Any combination of active agents.

Specifically, specific examples of the aforementioned surfactants may include, but are not limited to, polyethoxylated alkyl ethers such as polyethoxylauryl ether, polyethoxystearyl ether, or polyethoxylated oleyl ether, etc. Polyoxyethylene alkyl ethers; polyethoxyalkyl phenyl ethers such as polyethoxy octyl phenyl ether or polyethoxy nonyl phenyl ether; polyethylene glycol dilaurate or polyethylene glycol di Polyethylene glycol diesters such as stearate; sorbitan fatty acid esters; fatty acid-modified polyesters; or tertiary amine-modified polyurethanes. The above-mentioned surfactants can be used alone or in combination.

Specific examples of the surfactant may include products manufactured by Shin-Etsu Chemical Industries under the trade name of KP; manufactured by Dow Corning Toray Co., Ltd. under the trade name of SF-8427 Product; manufactured by the oleochemical industry of Kyoeisha under the trade name of Polyflow; manufactured by Tochem Products Co., Ltd. with the trade name of Aifudo A product of F-Top; manufactured by Dainippon Ink Chemical Industry under the trade name Products of Megafac; manufactured by Sumitomo 3M under the trade name Fluorade; manufactured by Asahi Glass under the trade name Asahi Guard; or manufactured by Asahi Glass Products manufactured by the company under the trade name Surflon. The aforementioned surfactants may be used alone or in combination of two or more.

Based on 100 parts by weight of polysiloxane (A), the amount of white pigment (E) used is usually 70 to 600 parts by weight, preferably 80 to 550 parts by weight, and more preferably 85 to 500 parts by weight.

Potential Antioxidant (F)

The negative-type white photosensitive resin composition of the present invention may contain a latent antioxidant (F), and the latent antioxidant (F) may have a structure represented by the following formula (II):

、-S-S-、-SO₂-或上述基團之任意組合所取代，其中Y₅代表氫原子或碳數為1至8之烷基；a代表1至3之整數，當a大於1時，複數個Y₂可以彼此鍵結形成苯環或萘環，且複數個Y₂可為相同或不同；b代表1至3之整數，當b大於1時，複數個Y₃可為相同或不同；d代表1至10之整數；Y₄代表單鍵、氮原子、氧原子、硫原子、磷原子、如下式(II-1)所示之基團、

、

、-NH-CO-、-CO-NH-、

、

、-OY₆、-SY₆、-NY₆Y₇、-PY₆Y₇、與d具有相同數目之價數且經取代或不取代的碳數為1至120之脂肪族烴基、經取代或不取代的碳數為6至35之芳香環族烴基或者經取代或不取代且碳數為2至35之含雜環基團；

In formula (II), ring A represents a five-membered or six-membered alicyclic, aromatic or heterocyclic ring; Y ₁ and Y ₂ independently represent hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, Carboxyl group, substituted or unsubstituted alkyl group with 1 to 40 carbon atoms, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms or heterocyclic group with 2 to 20 carbon atoms group; Y ₃ represents an alkyl group with a carbon number of 1 to 20, an alkenyl group with a carbon number of 2 to 20, an aryl group with a carbon number of 6 to 20, an aralkyl group with a carbon number of 7 to 20, and an aralkyl group with a carbon number of 2 to 20 20 containing a heterocyclic group or a trialkylsilyl group; the methylene group in the alkyl group or aralkyl group represented by Y ₁ , Y ₂ and Y ₃ can be selected from -C=C-, -O- , -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, - O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NY ₅ -,

, -SS-, -SO ₂ - or any combination of the above-mentioned groups, wherein Y ₅ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 8; a represents an integer of 1 to 3, when a is greater than 1, A plurality of Y ₂ can be bonded to each other to form a benzene ring or a naphthalene ring, and a plurality of Y ₂ can be the same or different; b represents an integer from 1 to 3, and when b is greater than 1, a plurality of Y ₃ can be the same or different; d represents an integer from 1 to 10; Y ₄ represents a single bond, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following formula (II-1),

,

, -NH-CO-, -CO-NH-,

,

, -OY ₆ , -SY ₆ , -NY ₆ Y ₇ , -PY ₆ Y ₇ , a valence of the same number as d and a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 120, substituted or Unsubstituted aromatic ring hydrocarbon group with carbon number of 6 to 35 or substituted or unsubstituted and heterocyclic group containing carbon number of 2 to 35;

、-S-S-、-SO₂-、氮原子或上述基團之任意組合所取代；前述之芳香環或雜環可以與其他環縮合；當Y₄為氮原子、磷原子或如式(II-1)所示之基團時，d代表3；當Y₄為氧原子或硫原子時，d代表2；當Y₄為單鍵、

、

、-NH-CO-、-CO-NH-、

或

時，d代表2；當Y₄為-OY₆、-SY₆、-NY₆Y₇或-PY₆Y₇時，d為1；Y₄也可以與環A形成環基團。 Y ₆ and Y ₇ respectively represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 35, a substituted or unsubstituted hydrocarbon group with a carbon number of 6 to 35 containing an aromatic ring, or a substituted or unsubstituted hydrocarbon group containing an aromatic ring. Unsubstituted heterocyclic group containing 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring and the methylene group in the heterocyclic group can be selected from -C=C-, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O -CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NY ₅ -,

, -SS-, -SO ₂ -, nitrogen atom or any combination of the above-mentioned groups; the aforementioned aromatic ring or heterocyclic ring can be condensed with other rings; when Y ₄ is a nitrogen atom, a phosphorus atom or as in formula (II- 1) In the group shown, d represents 3; when Y ₄ is an oxygen atom or a sulfur atom, d represents 2; when Y ₄ is a single bond,

,

, -NH-CO-, -CO-NH-,

or

, d represents 2; when Y ₄ is -OY ₆ , -SY ₆ , -NY ₆ Y ₇ or -PY ₆ Y ₇ , d is 1; Y ₄ can also form a ring group with ring A.

In the aforementioned formula (II), Y ₄ may represent a specific atom or group with a valence of d, or a structure bonded with d specific groups. wherein the d specific groups may be the same or different. d may be an integer from 1 to 10. From the viewpoint of ease of synthesis, d is preferably an integer of 2 to 6.

When ring A in the aforementioned formula (II) represents a five-membered ring, its specific examples can include but are not limited to five-membered alicyclic rings such as cyclopentane, five-membered aromatic rings such as cyclopentadiene or ferrocene (Ferrocene), Or a five-membered heterocycle of furan, thiophene, pyrrole, pyrrolidine, pyrazolidine, pyrazole, imidazole, imidazolidine, oxazole, isoxazole, isoxazolidine, thiazole, isothiazole or isotetrahydrothiazole; When ring A in the aforementioned formula (II) represents a six-membered ring, its specific examples may include, but are not limited to, six-membered alicyclic rings such as cyclohexane, benzene ring, naphthalene ring, anthracene ring, fluorene ring, perylene ring or pyrene ring, etc. A six-membered aromatic ring, or a six-membered heterocyclic ring such as piperidine, piperazine, morpholine, thiomorpholine, pyridine, pyrazine, pyrimidine, pyridazine or triazine; the ring A can also be combined with other cyclic structures Condensed or substituted. The cyclic structure formed by condensation or substitution may include, but is not limited to, quinoline, isoquinoline, indole, julolidine, benzoxazole, benzotriazole or azulene and other structures .

The aforementioned Y ₁ and Y ₂ may represent halogen atoms such as fluorine, chlorine, bromine, iodine and the like.

When Y ₁ and Y ₂ represent an alkyl group with a carbon number of 1 to 40 and Y ₃ represents an alkyl group with a carbon number of 1 to 20, specific examples thereof may include but are not limited to methyl, ethyl, propyl, isopropyl butyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methyl ring Hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, 1-octyl, isooctyl, tert-octyl or adamantyl and the like.

When Y ₁ and Y ₂ represent an oxyalkyl group with a carbon number of 1 to 40, specific examples thereof may include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tertiary Butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyl oxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy or tert-octyloxy and the like.

When Y ₁ and Y ₂ represent substituted or unsubstituted alkyl and oxyalkyl groups with a carbon number of 1 to 40, an aryl group with a carbon number of 6 to 20, an aralkyl group with a carbon number of 7 to 20 and a carbon number When it is a heterocyclic group of 2 to 20, its specific examples may include, but are not limited to, ethylenically unsaturated groups such as vinyl, propenyl, acrylic or methacrylic; fluorine, chlorine, bromine, iodine, etc. halogen atom; acetyl, 2-chloroacetyl, propionyl, octyl, acryl, methacryloyl, phenylcarbonyl (benzyl), phthalyl, 4- Trifluoromethylbenzyl, neopentyl, salicyl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl or Carboxylic group such as carboxyl group; carboxyl group such as acetoxyl group or benzyloxy group; amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2 -Ethylhexylamino, dodecylamino, anilino, chloroanilino, toluidine, methoxyanilino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino , methoxycarbonyl, phenoxycarbonyl, acetylamino, benzylamino, methylamino, neopentyl, lauryl, aminocarbamoyl, N,N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy Carbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, etc. Substituted amino; sulfoamino, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, mercapto, imino, carbamate, phosphonic acid, phosphoric acid or its carboxyl, sulfo, phosphine Acid and phosphoric acid salts.

When Y ₃ represents an alkenyl group having 2 to 20 carbon atoms, specific examples thereof may include, but are not limited to, vinyl group, allyl group, butenyl group, or propenyl group, and the like.

When Y ₁ , Y ₂ and Y ₃ represent an aromatic group having 6 to 20 carbon atoms, specific examples thereof may include, but are not limited to, phenyl, naphthyl, anthracenyl, and the like.

When Y ₁ , Y ₂ and Y ₃ represent an aralkyl group having 7 to 20 carbon atoms, specific examples thereof may include, but are not limited to, benzyl, fluorenyl, indenyl or 9-fluorenyl and the like.

When Y ₁ , Y ₂ and Y ₃ represent a heterocyclic group containing 2 to 20 carbon atoms, specific examples thereof include but are not limited to pyridine, pyrimidine, pyridazine, piperidine, pyran, pyrazole, triazine, Pyrrole, quinoline, isoquinoline, imidazole, benzimidazole, triazole, furyl, benzofuran, thiophene, thiophenyl, benzothiophene, thiadiazole, thiazolyl, benzothiazole, oxazole, benzene Isoxazole, isothiazole, isoxazole, indolyl, 2-pyrrolidone-1-yl, 2-piperidinone-piperazin-1-yl, 2,4-di-oxo-imidazolidine-3-yl Or 2,4-di-oxo-oxazolidinone-3-yl, etc.

When Y ₃ represents a trialkylsilyl group, specific examples thereof may include, but are not limited to, trimethylsilane, triethylsilane, or ethyldimethylsilane.

When Y ₄ represents a substituted or unsubstituted monovalent aliphatic hydrocarbon group with a carbon number of 1 to 120, a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 35 represented by Y ₄ , Y ₆ and Y ₇ Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-amyl , cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, n-heptyl Alkyl of octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl or decyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy , sec-butyl, tert-butyl, isobutyl, pentyloxy, isopentyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy , alkoxy groups such as n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy or decyloxy; methylthio, ethylthio, propylthio, butyl Thio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, Thio groups such as tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio or 2-ethylhexylthio; or vinyl, 1-methylvinyl, 2-methylvinyl , 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexyl Alkenyl groups such as alkenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl or tridecenyl.

When Y ₄ represents a substituted or unsubstituted divalent to tenvalent aliphatic hydrocarbon group with a carbon number of 1 to 120, specific examples thereof may include, but are not limited to, divalent corresponding to the specific examples of the aforementioned monovalent aliphatic hydrocarbon group to ten-valent functional groups.

When Y ₄ , Y ₆ and Y ₇ represent a substituted or unsubstituted monovalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, specific examples thereof include but are not limited to benzyl, phenethyl, diphenyl Aralkyl groups such as methyl, triphenylmethyl, styryl or cinnamyl; aromatic groups such as phenyl or naphthyl; aryloxy groups such as phenoxy or naphthyloxy; phenylthio or naphthylthio arylthio groups such as bases.

When Y ₄ represents a substituted or unsubstituted divalent to tenvalent aromatic ring-containing hydrocarbon group with a carbon number of 6 to 35, specific examples thereof may include, but are not limited to, those corresponding to the specific examples of the aforementioned monovalent aromatic ring-containing hydrocarbon group Divalent to tenvalent functional groups.

When Y ₄ , Y ₆ and Y ₇ represent a substituted or unsubstituted monovalent heterocyclic group containing 2 to 35 carbon atoms, specific examples thereof include but are not limited to pyridyl, pyrimidinyl, pyridazinyl, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, benzofuranyl, thienyl , phenylthio, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidone- 1-yl, 2-piperidinone-piperazin-1-yl, 2,4-di-oxo-imidazolidin-3-yl, 2,4-di-oxo-oxazolidin-3-yl or benzene and triazolyl, etc.

When Y ₄ represents a substituted or unsubstituted divalent to tenvalent heterocyclic group containing 2 to 35 carbon atoms, specific examples thereof may include but are not limited to those corresponding to the specific examples of the aforementioned monovalent heterocyclic group Divalent to tenvalent functional groups.

The aforementioned substituents may include, but are not limited to, ethylenically unsaturated groups such as vinyl, propenyl, acrylic or methacrylic; halogen atoms such as fluorine, chlorine, bromine or iodine; acetyl, 2-chloro Acetyl, propionyl, octyl, acryl, methacryloyl, phenylcarbonyl (benzyl), phthalyl, 4-trifluoromethylbenzyl, neopentyl Acetyl, salicyl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl or carbamoyl, etc.; acetyloxy benzyl or benzyloxy, etc.; amino, ethylamino, dimethylamino, diethylamino group, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chloroanilino, toluidine, methoxyaniline, N-methyl-aniline, diphenylamino , naphthylamino, 2-pyridylamino, methoxycarbonyl, phenoxycarbonyl, acetylamino, benzylamino, carboxylamino, neopentyl, lauryl, carbamate, N, N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxy N-methyl-methoxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methanesulfonylamino, butanesulfonylamino Or substituted amino groups such as benzenesulfonylamino; or its carboxyl, sulfo, phosphonic acid and phosphoric acid salts, and the aforementioned substituents may be further substituted. In addition, carboxyl and sulfo groups can form salts.

Based on the advantages of easy synthesis and better thermal xanthosis resistance, the aforementioned latent antioxidants represented by formula (II) can be compounds represented by the following formulas (II-2) to (II-4):

In formula (II-2), ring A ₁ represents a six-membered alicyclic, aromatic or heterocyclic ring; Y ₈₁ , Y ₈₂ , Y ₈₃ , Y ₈₄ and Y ₈₅ independently represent a hydrogen atom, a halogen atom, cyano, hydroxyl, nitro, carboxyl, substituted or unsubstituted alkyl with 1 to 40 carbons, aryl with 6 to 20 carbons, aralkyl with 7 to 20 carbons, carbon number of 2 to 20 containing heterocyclic groups or -OY ₂ ; at least one of Y ₈₁ , Y ₈₂ , Y ₈₃ , Y ₈₄ and Y ₈₅ is not a hydrogen atom; and the definitions of Y ₂ and Y ₃ are as described above;

In formula (II-3), Y ₄₁ represents a group represented by the following formula (i); Y ₈₆ , Y ₈₇ , Y ₈₈ and Y ₈₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group group, carboxyl group, substituted or unsubstituted alkyl group with 1 to 40 carbon atoms, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms, or heterocyclic group with 2 to 20 carbon atoms Ring group; at least one of Y ₈₆ , Y ₈₇ , Y ₈₈ and Y ₈₉ is not a hydrogen atom; the ring A ₁ is as defined above; and Y ₃ is as defined above; *-Z ₁ -Y ₄₁₁ -Z ₂ -* (i)

、

、二價之碳數為1至35的脂肪族烴基、碳數為6至35的芳香環族烴基或碳數為2至35的含雜環基，其中其可具有取代基，且該取代基如下式(II-3-1)至式(II-3-3)所示；該脂肪族烴基可為-O-、-S-、-CO-、-COO-、-OCO-或-NH-，或者其可藉 由與相鄰之氧原子組合而中斷鍵結；G₁與G₂分別獨立地代表氫原子、碳數為1至8之烷基、碳數為6至20之芳香基或碳數為7至20之芳烷基；Z₁及Z₂分別獨立地代表單鍵、-O-、-S-、

、-CO-O-、-O-CO-、-SO₂-、-S-S-、-SO-或

；G₃及G₄分別獨立地代表氫原子、經取代或不取代且碳數為1至35之脂肪烴基、碳數為6至35之芳香環族烴基、碳數為2至35之含雜環基團；

In formula (i), Y ₄₁₁ represents

,

, a divalent aliphatic hydrocarbon group with a carbon number of 1 to 35, an aromatic ring hydrocarbon group with a carbon number of 6 to 35 or a heterocyclic group with a carbon number of 2 to 35, which may have a substituent, and the substituent As shown in the following formulas (II-3-1) to (II-3-3); the aliphatic hydrocarbon group may be -O-, -S-, -CO-, -COO-, -OCO- or -NH- , or it can be interrupted by combining with adjacent oxygen atoms; G ₁ and G ₂ independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 8, an aryl group with a carbon number of 6 to 20, or Aralkyl with 7 to 20 carbon atoms; Z ₁ and Z ₂ independently represent single bond, -O-, -S-,

, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO- or

; G ₃ and G ₄ independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 35, an aromatic ring hydrocarbon group with a carbon number of 6 to 35, an impurity-containing hydrocarbon group with a carbon number of 2 to 35 ring group;

In formula (II-3-1), Q ₁ represents a hydrogen atom, or a phenyl group substituted with an alkyl group having a carbon number of 1 to 10 or a cycloalkyl group having a carbon number of 3 to 10; P ₁ represents a carbon number of 1 to 10 alkyl groups, 1 to 10 carbon alkoxy groups, 2 to 10 carbon alkenyl groups or halogen atoms; the alkyl groups, alkoxy groups and alkenyl groups may be substituted by halogen atoms; m represents an integer from 0 to 5;

In formula (II-3-3), Q ₂ and P ₂ each independently represent an alkyl group substituted or unsubstituted with a halogen atom and having 1 to 10 carbon atoms, substituted or unsubstituted with a halogen atom and having a carbon number of 6 Aryl group to 20, aryloxy group substituted or unsubstituted with halogen atom and carbon number of 6 to 20, arylthio group substituted or unsubstituted with halogen atom and carbon number of 6 to 20, substituted or unsubstituted with halogen atom Aromatic alkenyl substituted with 6 to 20 carbon atoms, aromatic alkyl substituted or unsubstituted with halogen atoms and with 7 to 20 carbon atoms, substituted or unsubstituted with halogen atoms and containing 2 to 20 carbon atoms Heterocyclic groups or halogen atoms; the alkyl moiety in the alkyl and aromatic alkyl groups may be interrupted by unsaturated bonds, -O- or -S-; Q ₂ may form and be adjacent to the cyclic structure; p represents an integer from 0 to 4; q represents an integer from 0 to 8; r represents an integer from 0 to 4; s represents an integer from 0 to 4; and the sum of r and s is an integer from 2 to 4;

In formula (II-4), d is 2 to 6; when d is 2, Y ₄₂ is a group represented by the aforementioned formula (i); when d is 3, Y ₄₂ is represented by the following formula (ii) when d is 4, Y ₄₂ is a group represented by the following formula (iii); when d is 5, Y ₄₂ is a group represented by the following formula (iv); when d is 6, Y ₄₂ is a group represented by the following formula (v); Y ₉₁ , Y ₉₂ , Y ₉₃ and Y ₉₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, substituted or unsubstituted and an alkyl group with a carbon number of 1 to 40, an aryl group with a carbon number of 6 to 20, an aralkyl group with a carbon number of 7 to 20, or a heterocyclic group with a carbon number of 2 to 20; Y ₉₁ , Y ₉₂ At least one of , Y ₉₃ and Y ₉₄ is not a hydrogen atom; the definition of ring A ₁ is as described above; the definition of Y ₃ is as described above;

、-CO-O-、-O-CO-、-SO₂-、-S-S-、-SO-、

、

、經取代或不取代的碳數為1至35之脂肪族烴基、經取代或不取代的碳數為6至35的芳香環族烴基或經取代或不取代的碳數為2至35的含雜環基；G₃代表氫原子、經取代或不取代之碳數為1至35之脂肪族烴基、經取代或不取代之碳數為6至35的芳香環族烴基或經取代或不取代之碳數為2至35的含雜環基；該脂肪族烴基可被碳-碳雙鍵結合、-O-、-CO-、-O-CO-、-CO-O-或-SO₂-中斷鍵結；

In formula (ii), M ₁ can be a trivalent aliphatic hydrocarbon group with a carbon number of 3 to 35, an aromatic ring hydrocarbon group with a carbon number of 6 to 35 or a heterocyclic group with a carbon number of 2 to 35; Z ₁ , Z ₂ and Z ₃ independently represent a single bond, -O-, -S-,

, -CO-O-, -O-CO-, -SO ₂ -, -SS-, -SO-,

,

, a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 35, a substituted or unsubstituted aromatic ring hydrocarbon group with a carbon number of 6 to 35, or a substituted or unsubstituted carbon number of 2 to 35 containing Heterocyclic group; G ₃ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 35, a substituted or unsubstituted aromatic ring hydrocarbon group with a carbon number of 6 to 35, or a substituted or unsubstituted hydrocarbon group A heterocyclic group containing 2 to 35 carbon atoms; the aliphatic hydrocarbon group may be bonded by carbon-carbon double bonds, -O-, -CO-, -O-CO-, -CO-O- or -SO ₂ - break key;

In formula (iii), M ₂ can be a carbon atom, a tetravalent aliphatic hydrocarbon group with a carbon number of 1 to 35, an aromatic ring hydrocarbon group with a carbon number of 6 to 35, or a heterocyclic ring with a carbon number of 2 to 35 group; the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-; Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently represented Groups in the same range as the groups represented by Z ₁ to Z ₃ in the aforementioned formula (ii);

In formula (iv), M ₃ can represent a pentavalent aliphatic hydrocarbon group with a carbon number of 2 to 35, an aromatic ring hydrocarbon group with a carbon number of 6 to 30, or a heterocyclic group with a carbon number of 2 to 30; the aliphatic group The family of hydrocarbon groups may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-; Z ₁ , Z ₂ , Z ₃ , Z ₄ or Z ₅ independently represent Groups in the same range as the groups represented by Z ₁ to Z ₃ in the aforementioned formula (ii);

In formula (v), M ₄ can be a hexavalent aliphatic hydrocarbon group with a carbon number of 2 to 35, an aromatic ring hydrocarbon group with a carbon number of 6 to 35 or a heterocyclic group with a carbon number of 2 to 35; the Aliphatic hydrocarbon groups can be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-; Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ or Z ₆ respectively independently represent groups in the same range as the groups represented by Z ₁ to Z ₃ in the aforementioned formula (ii).

In the compound represented by the aforementioned formula (II), Y ₃ may be an alkyl group having 1 to 20 carbon atoms, and the terminal methylene group where Y ₃ is bonded to an oxygen atom may be substituted by -CO-O-. Among them, when Y ₃ is an alkyl group with a carbon number of 1 to 8, and the terminal -CO-O- of Y ₃ is bonded to an oxygen atom, its functional benefit as a potential additive is better.

Next, Y ₈₁ to Y ₈₉ and Y ₉₁ to Y ₉₄ of Y ₁ and/or Y ₂ in formula (II-2) to formula (II-4) may represent a hydrogen atom or an alkane having 1 to 40 carbon atoms The group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

The manufacturing method of the aforementioned formula (II) is not particularly limited, and its manufacturing method can be, for example, Japanese Patent Publication No. 1982-111375, Japanese Patent Publication No. 1991-173843, Japanese Patent Publication No. 1994-128195, and Japanese Patent Publication No. 1994-128195. No. 1995-206771, Japanese Patent Publication No. 1995-252191 or Japanese Patent Publication No. 2004-501128 using phenolic compounds, acid anhydrides, acid chlorides, tert-Butoxycarbonyl (tert-Butoxycarbonyl; BOC) chemical reagents, A production method of reacting an alkyl halide compound, a silyl chloride compound and an allyl ether compound.

Based on the total usage amount of polysiloxane (A) is 100 parts by weight, the usage amount of the latent antioxidant (F) represented by formula (II) can be 0.5 to 10 parts by weight, preferably 0.8 Parts by weight to 8 parts by weight, and more preferably 1 part by weight to 6 parts by weight.

If the negative-type white photosensitive resin composition of the present invention does not contain the latent antioxidant (F) represented by formula (II), the prepared negative-type white photosensitive resin composition has poor thermal yellowing resistance.

Additive (G)

On the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may optionally further add an additive (G). Specific examples of the additive (G) may include, but are not limited to, surfactants, fillers, adhesion promoters, antioxidants, ultraviolet absorbers or anti-aggregation agents.

The aforementioned surfactant contributes to improving the coatability of the photosensitive resin composition. The surfactant may include cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, polysiloxane-based surfactant, fluorine-based surfactant, or any of the above surfactants. random combination. Specific examples and preferred embodiments of the surfactant are the same as the specific examples and preferred embodiments described in the aforementioned white pigment (E), and will not be repeated here.

Specific examples of the aforementioned filler can include glass, aluminum, or the like.

Specific examples of the aforementioned adhesion promoters may include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2- Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-amine 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidol Propylmethyldiethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropionyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxy Propyltrimethoxysilane, bis-1,2-(trimethoxysilyl)ethane, commercially available products under the trade name SZ 6030 (Dow Corning Toray Silicone), commercially available products under the trade names KBE-903, KBE-603, KBE-403, or KBM-403 (manufactured by Shin-Etsu Chemical), or any combination of the above.

Specific examples of the aforementioned antioxidants may include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or any combination of the above compounds.

Specific examples of the aforementioned ultraviolet absorbers may include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxy phenone or the above Any combination of compounds.

Specific examples of the aforementioned anti-aggregation agent may include sodium polyacrylate and the like.

Based on the total usage amount of the polysiloxane (A) being 100 parts by weight, the usage amount of the additive (G) can be 0 to 10 parts by weight, preferably 0 to 6 parts by weight, and more preferably 0 to 3 parts by weight.

Preparation method of negative white photosensitive resin composition

The negative-type white photosensitive resin composition of the present invention can be prepared, for example, by combining a polysiloxane (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), the white pigment (E) and the latent antioxidant (F) are placed in a stirrer and stirred to make them uniformly mixed into a solution state, and various additives (G) can be added as required to obtain the negative electrode of the present invention. Type white photosensitive resin composition.

Preparation method of white matrix

The preparation method of the white matrix of the present invention may include firstly coating the aforementioned negative-type white photosensitive resin composition on a substrate, and sequentially applying pre-baking, exposing, developing and post-baking treatments to form a white matrix. The substrate can be a transparent substrate, and it can include a glass substrate or a plastic substrate. Specific examples of the glass substrate may include alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass, or a glass substrate having a transparent conductive film on these glasses. Specific examples of the plastic substrate may include polyimide, polycarbonate, polymethyl methacrylate or polyethylene terephthalate. The substrate may be subjected to suitable pretreatment, such as chemical treatment with a silane crosslinker, plasma treatment, ion plating, sputtering, gas evaporation or vacuum vapor deposition.

Among them, the negative white photosensitive resin composition mixed into a solution state can be applied by coating methods such as spin coating, casting coating, ink-jet coating (ink-jet) or roll coating. on the substrate to form a coating film. After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and the remaining solvent is completely removed by a pre-bake method to form a pre-bake coating film. Among them, the conditions for drying under reduced pressure and pre-baking vary according to the types and proportions of the ingredients. Generally speaking, drying under reduced pressure is performed under a pressure of less than 200 mmHg for 1 second to 60 seconds, and prebaking is performed by heating the coating film at a temperature of 70° C. to 110° C. for 1 minute to 15 minutes.

After pre-baking, the above-mentioned pre-baking coating film is exposed to light with a mask having a specific pattern. The light used in the exposure process may be, for example, ultraviolet rays such as g-line, h-line or i-line. The UV irradiation device may be a (ultra) high pressure mercury lamp or a metal halide lamp.

Then, at a temperature of 21° C. to 25° C., the above-mentioned exposed pre-baking coating film is immersed in a developing solution to remove unnecessary parts of the pre-baking coating film, thereby forming a specific pattern on the substrate. . Here, the time (development time) for immersion in the developing solution can be, for example, 15 seconds to 5 minutes.

Specific examples of the developer may include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, diethylamine Aqueous solutions of basic compounds such as methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, quaternary or 1,8-diazabicyclo[5.4.0]-7-undecene.

It is worth mentioning that too high developer concentration will damage the specific pattern formed or reduce the resolution of the specific pattern; and too low developer concentration will cause poor development, resulting in the specific pattern not being formed, or the unexposed part. The composition remained. Therefore, the concentration of the developer will affect the formation of a specific pattern after exposure of the subsequent negative-type white photosensitive resin composition. The concentration of the developer may be 0.001 to 10 weight percent, preferably 0.005 to 5 weight percent, and more preferably 0.01 to 1 weight percent.

After developing the pre-baked coating film, the substrate with the specific pattern is washed with water, and the specific pattern is air-dried with compressed air or compressed nitrogen. After air-drying, the substrate is subjected to post-bake treatment using a heating device such as a hot plate or an oven. The post-baking temperature is usually 100°C to 280°C, and the heating time is 1 minute to 15 minutes. Removal of volatiles from the coating film by post-bake treatment component, and the unreacted ethylenically unsaturated double bond in the coating film undergoes a thermosetting reaction. After the above steps, a white matrix can be formed on the substrate.

Preparation method of color filter

The present invention further provides a color filter comprising the aforementioned white matrix.

The manufacturing method of a color filter is to form a white matrix on a substrate first. Next, in the same way, repeat the above-mentioned steps three times with the photosensitive resin composition of various colors (for example, including red, green, and blue) at the predetermined pixel position, and then the pixel of the color filter can be obtained. Shading layer. Next, an indium-tin oxide (Indium-Tin Oxide; ITO) vapor-deposited film is formed on the pixel coloring layer, and if necessary, the ITO vapor-deposited film is etched/wired to obtain a color filter for a reflective display device .

Manufacturing method of reflective display device

The present invention further provides a reflective display device comprising the aforementioned color filter.

The reflective display device of the present invention is a display device that utilizes an external ambient light source to reflect and then reflect to display an image. Specific examples of the reflective display device may include a reflective liquid crystal display, an electronic paper display, and the like. The structure of the electronic paper display and its manufacturing method are described below.

1A-1B are schematic cross-sectional views illustrating the structure of an electronic paper display according to an embodiment of the present invention.

Referring to FIG. 1A , the electronic paper display structure contains at least one or more particles, the particles have at least two or more different optical reflectances and charging characteristics, and the particles can constitute a display element. In this specific example, the electronic paper display 100 includes a first substrate 101 , a second substrate 102 , a first electrode 104 , a second electrode 106 , first particles 108 and second particles 110 . The first substrate 101 and the second substrate 102 are arranged so as to be opposite and parallel to each other. The first electrode 104 is disposed on the first substrate 101 , that is, close to the surface of the second substrate 102 . The first particles 108 are disposed above the first electrode 104 , that is, close to the surface of the second substrate 102 . The second electrode 106 is disposed below the second substrate 102 , that is, close to the surface of the first substrate 101 . The second particles 110 are disposed on the second electrode 106 , that is, close to the surface of the first substrate 101 . The first particles 108 are particles having a first color, such as white particles, and the second particles 110 are particles having a second color, such as black particles. The first particles 108 constitute the first display medium 112. In this specific example, the first display medium 112 is a white display medium; the second particles constitute the second display medium 114. In this specific example, the second display medium 114 is black. Display medium. The first particles 108 and the second particles 110 can move vertically between the first substrate 101 and the second substrate 102 due to the influence of the electric field generated by the voltage applied between the first electrode 104 and the second electrode 106 . When the user sees the first display medium 112, the color of the first display medium 112 is displayed, in this specific example, for example, white. When the user sees the second display medium 114, the color of the second display medium 114 is displayed, in this specific example, for example, black.

Referring to FIG. 1B , the electronic paper display 100a may also have a separation wall 116 (hydrophilic rib). The partition wall is disposed between the first substrate 101 and the second Between the two substrates 102 , the space between the first substrate 101 and the second substrate 102 is divided into a plurality of cells 118 .

FIG. 2 is a schematic cross-sectional view illustrating the structure of an electronic paper display according to an embodiment of the present invention.

Referring to FIG. 2 , the electronic paper display structure contains more than one kind of particles, the particles have optical reflectivity and charging characteristics, and the particles can constitute a display element. In this specific example, the electronic paper display 200 includes a first substrate 201 , a second substrate 202 , a first electrode 204 , a second electrode 206 , first particles 208 , a partition wall 216 and a color plate 220 . The first substrate 201 and the second substrate 202 are arranged so as to be opposite and parallel to each other. The first electrode 204 is disposed on the first substrate 201 , that is, close to the surface of the second substrate 202 . The first particles 208 are disposed above the first electrode 204 , that is, close to the surface of the second substrate 202 . The second electrode 206 is disposed below the second substrate 202 , that is, close to the surface of the first substrate 201 . The first particles 208 are particles having a first color, such as white particles. The first particles 208 constitute the first display medium 212. In this specific example, the first display medium 212 is a white display medium. The color plate 220 is disposed below the first electrode 204 , that is, on the surface opposite to the first particle 208 . The color plate 220 has a second color, eg, black. The partition wall 216 is disposed between the first substrate 201 and the second substrate 202 , and partitions the space between the first substrate 201 and the second substrate 202 into a plurality of lattices 218 . The first particles 208 can move in a diagonal direction between the first substrate 201 and the second substrate 202 due to the influence of the electric field generated by the voltage applied between the first electrode 204 and the second electrode 206 . When the user sees the first display medium 212, the color of the first display medium 212 is displayed, in this specific example, for example, white, and When the user sees the color plate 220 disposed under the first electrode 204, the color of the color plate 220 is displayed, in this specific example, for example, black.

3A to 3D are schematic cross-sectional views illustrating the structure of an electronic paper display according to an embodiment of the present invention.

Referring to FIG. 3A , a media-driven electronic paper 300 a is shown including a first substrate 301 , a second substrate 302 , a plurality of first electrodes 304 , a plurality of second electrodes 306 , first particles 308 , second particles 310 and partition walls 316 . The first substrate 301 and the second substrate 302 are arranged so as to be opposite and parallel to each other. The plurality of first electrodes 304 are independently disposed on the first substrate 301 , that is, close to the surface of the second substrate 302 . The first particles 308 are disposed above the plurality of first electrodes 304 , that is, close to the surface of the second substrate 302 . The plurality of second electrodes 306 are independently disposed under the second substrate 302 , that is, close to the surface of the first substrate 301 . The second particles 310 are disposed on the plurality of second electrodes 306 , that is, close to the surface of the first substrate 301 . The first particles 308 are particles having a first color, such as white particles, and the second particles 310 are particles having a second color, such as black particles. The partition wall 316 is disposed between the first substrate 301 and the second substrate 302 , and partitions the space between the first substrate 301 and the second substrate 302 into a plurality of lattices 318 .

Referring to FIG. 3B , it is shown that at least one electrode of the media-driven electronic paper 300b can also be a linear electrode. The display medium driven electronic paper 300b has a similar structure to the display medium driven electronic paper 300a, wherein the first electrode 304 is a linear electrode, and the plurality of second electrodes 306 are arranged independently of each other. The display medium-driven electronic paper can also have a plurality of independent first electrodes and The one-line second electrode (not shown), or both the one-line first electrode and the one-line second electrode (not shown).

Referring to FIG. 3C , the first particles 308 and the second particles 310 of the media-driven electronic paper 300 c are shown arranged in a microcapsule 322 , and the microcapsules 322 are arranged on the first electrodes of the first substrate 301 and the second substrate 302 304 and the second electrode 306 . The first electrode 304 and the second electrode 306 may be a plurality of electrodes arranged independently of each other, or may be a line electrode (not shown).

Referring to FIG. 3D , it is shown that the media-driven electronic paper 300 d has a rotating sphere 324 disposed between the first electrode 304 and the second electrode 306 . The first electrode 304 and the second electrode 306 may be a plurality of electrodes arranged independently of each other, or may be a line electrode (not shown). The surface of the rotating ball 324 has a first part 324a and a second part 324b. The first portion 324a is a first color, and the second portion 324b is a second color. The rotating ball 324 can rotate between the first substrate 301 and the second substrate 302 due to the influence of the electric field generated by the voltage applied between the first electrode 304 and the second electrode 306 . When the user sees the first part 324a, the first color is displayed, in this specific example, for example, white, and when the user sees the second part 324b, the second color is displayed. In this specific example, For example black.

In the above-mentioned specific example, the display medium may also be composed of powder fluid.

4 is a schematic cross-sectional view of a colorized electronic paper display according to an embodiment of the present invention.

Referring to FIG. 4 , the colorized electronic paper display 400 includes a first substrate 401 , a second substrate 402 , a first electrode 404 , a plurality of second electrodes 406 , first particles 408 , second particles 410 , partition walls 416 , and a white matrix 426 and color filters 428R, 428G, 428B. The first substrate 401 and the second substrate 402 are arranged so as to be opposite and parallel to each other. The first electrode 404 is a linear electrode and is disposed on the first substrate 401 , that is, close to the surface of the second substrate 402 . The first particles 408 are disposed above the first electrode 404 , that is, close to the surface of the second substrate 402 . The plurality of second electrodes 406 are independently disposed under the second substrate 402 , that is, close to the surface of the first substrate 401 . The second particles 410 are disposed on the plurality of second electrodes 406 , that is, close to the surface of the first substrate 401 . The first particles 408 are particles with a first color, such as white particles, and the second particles 410 are particles with a second color, such as black particles. The first particles constitute the first display medium 412, in this specific example, the first display medium 412 is a white display medium; the second particles constitute the second display medium 414, in this specific example, the second display medium 414 is a black display medium. The partition wall 416 is disposed between the first substrate 401 and the second substrate 402 , and partitions the space between the first substrate 401 and the second substrate 402 into a plurality of lattices 418 . The white matrix 426 is disposed on the second substrate 402 at a position corresponding to the partition wall 416 . The color filters 428R, 428G, and 428B are, for example, three primary colors (red, green, and blue), respectively, and are respectively disposed on the second substrate 402 at positions corresponding to each lattice body 418 . When a voltage is applied between the first electrode 404 and the second electrode 406 to generate an electric field, the first display medium 412 and the second display medium 414 in the lattice move to both sides, thereby displaying colors. In addition, three lattices arranged with color filters 428R, 428G, and 428B can form a pixel unit. The lattice 418 contained in the pixel unit controls the brightness of the light source through the color filters 428R, 428G, and 428B through the movement of the respective independent display media, and is generated by the color mixing effect of the color filters 428R, 428G, and 428B. The purpose of various colors.

5A to 5C are schematic diagrams illustrating the flow of forming a color filter in an electronic paper display according to an embodiment of the present invention.

Referring to FIG. 5A , a conductive film 502 is formed on one surface of a substrate 501 . The substrate 501 may be a transparent substrate, including a glass substrate or a plastic substrate. The conductive film 502 can be a transparent conductive film, including an indium tin oxide film, an indium-zinc oxide (Indium-Zinc Oxide; IZO) film, and the like. The method of forming the conductive thin film 502 is, for example, physical vapor deposition (Physical Vapor Deposition; PVD) or chemical vapor deposition (Chemical Vapor Deposition; CVD). Taking the indium tin oxide film as an example, the formation method thereof is, for example, sputtering. More specifically, target ions are formed in a vacuum chamber using an indium tin oxide target, and the target ions are deposited on a substrate through a sputtering process to form an indium tin oxide film.

Next, referring to FIG. 5B , the conductive film 502 is patterned to form the electrode 504 .

Thereafter, referring to FIG. 5C , a white matrix 526 and color filters 506R, 506G, and 506B for red, green, and blue pixels are formed on the other side of the substrate. Wherein, the white matrix 526 is formed by the above-mentioned manufacturing method of the white matrix, and the other color pixels are formed by using the above-mentioned method of forming color filters to form the color filter segments 506R, 506R, 506R, 506R, 506G, 506B.

In order to prevent the patterned transparent electrodes and color filters from being damaged, a protective film (not shown in the figure) can be formed on the surface of the patterned electrode 504 and/or the surfaces of the color filters 506R, 506G, and 506B. ).

How to make a white border

The present invention further provides a white frame, which is formed by the aforementioned negative-type white photosensitive resin composition. FIG. 6 is a schematic cross-sectional view of a white frame according to an embodiment of the present invention.

Referring to FIG. 6 , the photosensitive resin composition of the present invention can also be used to manufacture a white frame. The manufacturing method of the white frame includes coating the photosensitive resin composition on the substrate 601 , and then performing vacuum drying, pre-baking, exposure, developing and post-baking treatments in sequence to form the white frame 602 . The substrate 601 may further be provided with a circuit 604 at the white frame 602 to conduct the touch signal. Wherein, the white frame 602 can completely shield the circuit 604 at the peripheral portion, thereby ensuring the flatness of the touch panel and protecting the peripheral circuits of the touch panel. Since the white frame is formed by using the photosensitive resin composition of the present invention, the related products such as the touch panel or the flat panel display can have a better appearance, and the compatibility of the appearance of the product is also greatly improved.

The following uses several embodiments to illustrate the application of the present invention, but it is not intended to limit the present invention. Those with ordinary knowledge in the technical field of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. retouch.

100/100a/200: Electronic Paper Display

101/102/201/202/301/302/401/402/501/601: Substrate

104/106/204/206/304/306/404/406/504: Electrodes

108/110/208/308/310/408/410: Particles

112/114/212/412/414: Display Media

116/216/316/416: Dividing walls

118/218/318/418: Lattice

220: Color Board

300a/300b/300c/300d: Display Media Driven Electronic Paper

322: Microcapsules

324: Rotate Sphere

324a: The first part of the surface of a rotating sphere

324b: Second part of the surface of a rotating sphere

400: Colorized Electronic Paper Display

426/526: White Matrix

428R/428G/428B/506R/506G/506B: Color filter

502: Conductive film

602: At the white border

604: Line

In order to have a more complete understanding of the embodiments of the present invention and the advantages thereof, please refer to the above description together with the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustrative purposes only. The relevant diagrams are described as follows:

[FIG. 1A] to [FIG. 1B] are schematic cross-sectional views showing the structure of an electronic paper display according to an embodiment of the present invention.

[FIG. 2] is a schematic cross-sectional view illustrating the structure of an electronic paper display according to an embodiment of the present invention.

[FIG. 3A] to [FIG. 3D] are schematic cross-sectional views showing the structure of an electronic paper display according to an embodiment of the present invention.

[FIG. 4] is a schematic cross-sectional view of a colorized electronic paper display according to an embodiment of the present invention.

[FIG. 5A] to [FIG. 5C] are schematic diagrams illustrating the flow of forming a color filter in an electronic paper display according to an embodiment of the present invention.

[FIG. 6] is a schematic cross-sectional view of a white frame according to an embodiment of the present invention.

Preparation of polysiloxane (A)

The following are the synthesis of the polysiloxanes (A) of Preparation Examples A-1 to A-6 according to Table 1.

Preparation Example A-1

In a three-necked flask with a volume of 500 ml, add 0.05 moles of 2-epoxypropylene butoxypropyltrimethoxysilane (2-oxetanyl butoxypropyltrimethoxysilane; TMSOX), 0.40 mol of methyltrimethoxysilane (MTMS), 0.30 mol of phenyltrimethoxysilane (PTMS), 0.25 mol of phenyltriethoxysilane (phenyltriethoxysilane) ; PTES) and 200 g of 4-hydroxy-4-methyl-2-pentanone (Diacetone Alcohol; DAA), stirred at room temperature, and added an aqueous oxalic acid solution (0.4 g oxalic acid/75 g water) within 30 minutes . Next, the flask was immersed in a 30°C oil bath and stirred for 30 minutes. Then, the oil bath was heated to 120°C over 30 minutes. When the temperature of the solution dropped to 110°C, the polymerization was continued for 6 hours with heating and stirring. Then, the solvent was removed by distillation to obtain the polysiloxane (A-1) of Preparation Example A-1.

Preparation Examples A-2 to A-6

Preparation Examples A-2 to A-6 use the same preparation method as the synthesis method of the polysiloxane of Preparation Example A-1, except that Preparation Examples A-2 to A-6 change the polysiloxane in the preparation examples A-2 to A-6. The kinds of raw materials, usage amount and reaction conditions, their formulations and reaction parameters are shown in Table 1 respectively, and will not be repeated here.

Preparation of photoinitiator (C)

Preparation Example C-1-1

Step 1: Synthesis of 2-(o-tolyl)acetyl chloride

Under a nitrogen atmosphere, 100 g of 2-(o-tolyl)acetic acid and 237 g of thorium chloride were added to the reaction flask, slowly heated to 95° C., and refluxed for 4 hours. After 4 hours, set up distillation equipment at the same temperature, In order to distill the sulfite chloride under normal pressure. After the reaction flask was cooled to room temperature, the residual sulfite chloride was removed by vacuum distillation equipment. The viscous liquid remaining after distillation is precipitated in petroleum ether, and the precipitate is filtered to obtain a precipitate of yellow crystals. The precipitate of yellow crystals was 112 g, and the yield was 71%.

Step 2: Synthesis of 1-(4-(phenylthio)phenyl)-2-o-tolylethanone (1-(4-(phenylthio)phenyl)-2-o-tolylethanone)

Under nitrogen atmosphere, 90.0 g of diphenyl sulfide was dissolved in 540 mL of anhydrous dichloromethane. After the reactant was cooled to 0°C, 66.34 grams of aluminum chloride was added. Then, when the internal temperature was 5°C or lower, 83.9 g of 2-(o-tolyl)acetidyl chloride was added dropwise. After stirring at the reaction temperature at room temperature for 5 hours, the internal temperature was lowered to below 0°C, 700 mL of ice water was added to the reactor, and the mixture was stirred for 1 hour. After phase separation, neutralization was performed with 1% sodium hydroxide (700 mL). After neutralization and washing, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator. Recrystallization from ethyl acetate gave 140 g of a white solid (yield 91%).

The third step: Synthesis of cis-2-hydroxyimino-1-(4-(phenylthio)phenyl)-2-o-tolyl ethyl ketone ((E)-(hydroxyimino)-1-(4- (phenylthio)phenyl)-2-o-tolylethanone)

540 mL of dimethylformamide was added to the reaction flask, and 90 g of the compound obtained in the second step was dissolved in dimethylformamide. When the reactant temperature was 15°C, 7.63 grams of sodium methoxide was slowly added. 36.42 grams of isoamyl nitrite was added dropwise to the reaction, maintaining the internal temperature at 15°C. After the dropwise addition was completed, the temperature was raised to 25°C and stirred for 8 hours. Then, add 700 mL of ethyl acetate and 700 mL of distilled water into the reactant and washed with water. After washing with water three times and removing dimethylformamide, it was neutralized with saturated calcium carbonate, and the organic layer was dried with magnesium sulfate. After distillation under reduced pressure, a liquid compound can be obtained. The liquid compound was added to a mixed solution of hexane and dichloromethane for recrystallization to obtain 70 g of pale yellow crystals (yield 71%).

The fourth step: Synthesis of cis-2-acetoxyimino-1-(4-(phenylthio)phenyl)-2-o-tolyl ethyl ketone ((E)-2-(acetoxyimino)-i -(4-(phenylthio)phenyl)-2-o-tolylethanone)

In a nitrogen atmosphere, and the internal temperature is 0 ℃, add 50 grams of the compound obtained in the third step, 300 mL of dichloromethane and 15.0 grams of triethylamine into the reaction flask, and add 11.6 grams of dissolved A solution of acetyl chloride in 20 mL of dichloromethane. After the internal temperature rose to 10°C or higher, the mixture was stirred for 3 hours. Then, the addition of water to the reaction solution was repeated to wash the organic layer. After distillation under reduced pressure, the obtained solid was added to a solution of petroleum ether and dichloromethane for recrystallization. After filtration, 50 g of light yellow solid can be obtained (yield 89%), and this light yellow solid is the photoinitiator represented by the aforementioned formula (I-1).

Preparation Example C-1-2

Step 1: Synthesis of 2-(o-tolyl)acetyl chloride

The synthesis method of 2-(o-tolyl)acetidyl chloride of Preparation Example C-1-2 is the same as the synthesis method of the first step of Preparation Example C-1-1, and will not be repeated here.

The second step: Synthesis of 1-(4-((4-(2-methylbenzyl)phenyl)thio)phenyl)-2-(o-tolyl)ethanone (1-(4- ((4-(2-methylbenzoyl)phenyl)thio)phenyl)-2-(o-tolyl)ethanone)

Under nitrogen atmosphere, 50.0 g of diphenyl sulfide was dissolved in 300 mL of anhydrous dichloromethane. After the reactant was cooled to 0°C, 36.87 grams of aluminum chloride was added. Then, 42.74 g of o-chlorotoluene was diluted with 80 mL of dichloromethane and added dropwise to the reaction flask. After stirring for 8 hours at the reaction temperature at room temperature, the internal temperature was lowered to below 0°C, and 36.87 g of aluminum chloride was added. Then, 46.62 g of 2-(o-tolyl)acetyl chloride was diluted with 80 mL of dichloromethane, and added dropwise to the reaction flask when the internal temperature was 5°C or lower. After stirring at the reaction temperature at room temperature for 5 hours, the internal temperature was lowered to below 0°C, 500 mL of ice water was added to the reactor, and the mixture was stirred for 1 hour. After phase separation, neutralization was performed with 1% sodium hydroxide (500 mL). After neutralization and washing, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator. Recrystallization from methanol gave 75 g of a white solid (yield 64%).

The third step: Synthesis of 1-(4-((4-(2-methylbenzyl)phenyl)sulfanyl)phenyl)-2-(o-tolyl)ethane-1,2-di Ketone (1-(4-((4-(2-methylbenzoyl)phenyl)thio)phenyl)-2-(o-tolyl)ethane-1,2-dione)

300 mL of dimethylformamide was added to the reaction flask, and 50 g of the compound obtained in the second step was dissolved in dimethylformamide. When the reaction temperature was 15°C, 3.09 grams of sodium methoxide was added. 13.82 g of isoamyl nitrite was added dropwise to the reactant, and the internal temperature was maintained. The temperature is 15℃. After the dropwise addition was completed, the temperature was raised to 25°C and stirred for 8 hours. Then, 400 mL of ethyl acetate and 400 mL of distilled water were added to the reactant, washed with water three times, and dimethylformamide was removed, neutralized with saturated calcium carbonate, and dried with magnesium sulfate. Floor. After distillation under reduced pressure, a liquid compound can be obtained. The liquid compound was added to a mixed solution of hexane and methanol for recrystallization to obtain 35 g of pale yellow crystals (yield 66%).

The fourth step: Synthesis of trans-2-acetoxyimino-1-(4-((4-(2-methylbenzyl)phenyl)thio)phenyl)-2-(ortho- Tolyl) ethyl ketone ((Z)-2-(acetoxyimino)-1-(4-((4-(2-methylbenzoyl)phenyl)thio)phenyl)-2-(o-tolyl)ethanone)

In a nitrogen atmosphere, and the internal temperature is 0 ℃, 30 grams of the compound obtained in the third step, 180 mL of dichloromethane and 6.7 grams of triethylamine were added to the reaction flask, and 5.21 grams of dissolved A solution of acetyl chloride in 10 mL of dichloromethane. After the internal temperature became 10°C or higher, the mixture was stirred for 3 hours. Then, the addition of water to the reaction solution was repeated to wash the organic layer. After distillation under reduced pressure, the obtained solid was added to a solution of n-hexane and dichloromethane for recrystallization. After filtration, 26 g of light yellow solid can be obtained (the yield is 79%), and this light yellow solid is the photoinitiator represented by the aforementioned formula (I-7).

Preparation Example C-1-3

Preparation example C-1-3 uses the same preparation method and steps as the synthesis method of the photoinitiator of preparation example C-1-1, the difference is that preparation example C-1-3 changes the photoinitiator in preparation example C-1-3. The types and amounts of raw materials used will not be repeated here. described. Wherein, the photoinitiator prepared in Preparation Example C-1-3 has the structure shown in the aforementioned formula (I-4).

Preparation Examples C-1-4 to C-1-6

Preparation Examples C-1-4 to C-1-6 use the same preparation method and steps as the synthesis method of the photoinitiator of Preparation Example C-1-2, except that Preparation Examples C-1-4 to C-1-6 C-1-6 changes the type and usage amount of the raw materials in the photoinitiator, which will not be repeated here. Wherein, the photoinitiator prepared in Preparation Example C-1-4 has the structure shown in the aforementioned formula (I-10); the photoinitiator prepared in Preparation Example C-1-5 has the aforementioned formula The structure shown in (I-12); and the photoinitiator prepared in Preparation Example C-1-6 has the structure shown in the aforementioned formula (I-16).

Preparation of latent antioxidants (F)

Preparation Example F-1

Add 0.01 mol of phenolic compound, 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine into the reaction flask, and mix them uniformly in a nitrogen atmosphere. At room temperature, 0.025 moles of 4-dimethylaminopyridine was added to the reaction flask, and the mixture was heated to 60°C and stirred for 3 hours. After cooling to room temperature, 150 g of ion-exchanged water was injected into the reaction solution, and 200 g of chloroform was added to perform extraction and separation of the oil-water layer. The organic layer was dried by adding anhydrous magnesium sulfate, then the solvent was removed, and 100 g of methanol was added for crystallization. After the obtained white powdery crystals were dried under reduced pressure at 60°C for 3 hours, the latent antioxidant of Preparation Example F-1 could be obtained, and its structure was shown in the following formula (II'-1):

Preparation Examples F-2 to F-4

Preparation Examples F-2 to F-4 use the same preparation method as the synthesis method of the latent antioxidant of Preparation Example F-1, except that Preparation Examples F-2 to F-4 change the potential antioxidants in the preparation examples F-2 to F-4. The types and amounts of raw materials used. The structures of the latent antioxidants prepared in Preparation Examples F-2 to F-4 are respectively shown in the following formulas (II'-2) to (II'-4):

Preparation of negative-type white photosensitive resin composition

The negative-type white photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared according to Table 2 below.

Example 1

100 parts by weight of the polysiloxane (A-1) of the above preparation example A-1, 30 parts by weight of pentaerythritol triacrylate (B-1), 3 parts by weight of the The photoinitiator (C-1-1), 120 parts by weight of strontium titanate (E-1) and 1.5 parts by weight of the latent antioxidant (F-1) of the above preparation example F-1 were added to 100 parts by weight In the solvent (D-1) of Propylene Glycol Monomethyl Ether Acetate (PGMEA), stir with a shaking stirrer to dissolve the above mixture in the solvent, and the negative white photosensitive material of Example 1 can be obtained. Resin composition. The obtained negative-type white photosensitive resin composition was evaluated by each of the following evaluation methods, and the results are shown in Table 2, and the detection methods of sensitivity and thermal yellowing resistance will be described later.

Examples 2 to 10 and Comparative Examples 1 to 3

Examples 2 to 10 and Comparative Examples 1 to 3 use the same preparation method as that of the negative-type white photosensitive resin composition of Example 1, except that Examples 2 to 10 and Comparative Examples 1 to 3 are The types and usage amounts of the raw materials in the negative-type white photosensitive resin composition were changed, and the formulations and evaluation results were shown in Table 2, which will not be repeated here.

Evaluation method

1. Heat-resistant yellowing

The negative-type white photosensitive resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were coated on a glass substrate by spin coating. Next, pre-bake at 100° C. for 2 minutes to obtain a pre-bake coating film with a thickness of about 15 μm. Then, the above-mentioned pre-baked coating film was placed under a line and space photomask [manufactured by Nibbon Filcon, Japan], and UV light (manufactured by M ^& R Nano) with an energy of 100 mJ/cm was used. Exposure machine manufactured by Technology, and its model is AG500-4N) for exposure. Next, develop with a potassium hydroxide aqueous solution with a concentration of 0.045% at 23° C. for 1 minute to remove the unexposed portion of the coating film on the substrate. After that, the glass substrate is washed with water, and the pre-baking coating film is placed at 230° C. for 30 minutes after baking, so that a white photoresist film with a specific pattern can be formed on the glass substrate.

The white photoresist film obtained above was measured for its b* value in the (L*, a*, b*) color system with a spectrophotometer CM-600d (manufactured by Konica Minolta Sensing) to obtain (b1*) . Then, after heat treatment at 230°C for 30 minutes, the b* value of the white photoresist film was measured again, and to get its (b2*). Then, the difference in b* value was calculated by the following formula (IV), and evaluated according to the following criteria: Δb=(b2*)-(b1*) formula (IV)

◎: △b≦0.5; ○: 0.5<△b≦1; △: 1<△b≦2.5; ×: 2.5<△b.

2. Sensitivity

The negative-type white photosensitive resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were coated on a glass substrate by spin coating. Next, pre-bake at 100° C. for 2 minutes to obtain a pre-bake coating film with a thickness of about 15 μm. Then, the above-mentioned pre-baked coating film was placed under a line and space photomask [manufactured by Nibbon Filcon, Japan], and UV light (manufactured by M ^& R Nano) with an energy of 100 mJ/cm was used. Exposure machine manufactured by Technology, and its model is AG500-4N) for exposure. Next, develop a potassium hydroxide aqueous solution with a concentration of 0.045% at 23°C for 1 minute to remove the unexposed part of the coating film on the substrate, and measure the film thickness of the patterned film. Finally, the following formula (V) is used to calculate the residual film rate , and evaluate the sensitivity according to the following criteria:

○: 90%<residual film rate; △: 80%<residual film rate≦90%; ×: residual film rate≦80%.

As can be seen from the results in Table 2, when the photoinitiator (C) of the composition of the negative-type white photosensitive tree of the present invention does not have the photoinitiator (C-1) shown in the formula (I) , the obtained negative-type white photosensitive resin composition has the defects of poor sensitivity and thermal yellowing.

Secondly, if the composition of the negative-type white photosensitive resin of the present invention does not contain the aforementioned latent antioxidant (F) represented by formula (II), the prepared negative-type white photosensitive resin composition has heat-resistant yellow Defects of poor degeneration.

In addition, if the polycondensation monomer of the polysiloxane (A) of the negative-type white photosensitive tree contains the silane monomer represented by the formula (III-1), the composition of the prepared negative-type white photosensitive resin The material has better heat-resistant yellowing.

It should be added that although the present invention uses specific compounds, compositions, reaction conditions, manufacturing processes, analytical methods or specific instruments as examples to illustrate the negative-type white photosensitive resin composition of the present invention and its application, the present invention belongs to the technical field. Anyone with ordinary knowledge will know that the present invention is not limited to this, and other compounds, compositions, reactions can also be used in the negative-type white photosensitive resin composition of the present invention and its application without departing from the spirit and scope of the present invention. conditions, processes, analytical methods or instruments.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the appended patent application.

Claims (9)

A negative-type white photosensitive resin composition, comprising: polysiloxane (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C), comprising the following formula (I) A photoinitiator (C-1):

In formula (I), X ₁ represents -O-, -S- or -Se-; X ₂ represents a phenyl group with 1 to 5 methyl groups; X ₃ represents an alkyl group with 1 to 10 carbon atoms, benzene group, or a cycloalkyl group with a carbon number of 3 to 6; X ₄ represents a hydrogen atom or

, and X ₅ represents

,

,

,

,

,

,

,or

, wherein X ₅₁ represents a methyl group or an ethyl group, and X ₅₂ represents a hydrogen atom or a methyl group; a solvent (D); a white pigment (E); and a latent antioxidant (F) represented by the following formula (II) :

In formula (II), ring A represents a five-membered or six-membered alicyclic, aromatic or heterocyclic ring; Y ₁ and Y ₂ independently represent hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, Carboxyl group, substituted or unsubstituted alkyl group with 1 to 40 carbon atoms, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms or heterocyclic group with 2 to 20 carbon atoms group; Y ₃ represents an alkyl group with a carbon number of 1 to 20, an alkenyl group with a carbon number of 2 to 20, an aryl group with a carbon number of 6 to 20, an aralkyl group with a carbon number of 7 to 20, and a carbon number of 2 to 20 containing a heterocyclic group or a trialkylsilyl group; the methylene group in the alkyl or aralkyl represented by Y ₁ , Y ₂ and Y ₃ can be selected from -C=C-, -O -, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NY ₅ -,

, -SS-, -SO ₂ - or any combination of the above-mentioned groups, wherein Y ₅ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 8; a represents an integer of 1 to 3, when a is greater than 1, A plurality of Y ₂ can be bonded to each other to form a benzene ring or a naphthalene ring, and a plurality of Y ₂ can be the same or different; b represents an integer from 1 to 3, and when b is greater than 1, a plurality of Y ₃ can be the same or different; d represents an integer from 1 to 10; Y ₄ represents a single bond, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following formula (II-1),

,

, -NH-CO-, -CO-NH-,

,

, -OY ₆ , -sY ₆ , -NY ₆ Y ₇ , -PY ₆ Y ₇ , a valence of the same number as d and a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 120, substituted or Unsubstituted aromatic ring hydrocarbon group with carbon number of 6 to 35 or substituted or unsubstituted and heterocyclic group containing carbon number of 2 to 35;

Y ₆ and Y ₇ respectively represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group with a carbon number of 1 to 35, a substituted or unsubstituted hydrocarbon group with a carbon number of 6 to 35 containing an aromatic ring, or a substituted or unsubstituted hydrocarbon group containing an aromatic ring. Unsubstituted heterocyclic group containing 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the hydrocarbon group containing an aromatic ring and the methylene group in the heterocyclic group can be selected from -C=C-, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O -CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NY ₅ -,

, -SS-, -SO ₂ -, nitrogen atom or any combination of the above-mentioned groups; the aforementioned aromatic ring or heterocyclic ring can be condensed with other rings; when Y ₄ is a nitrogen atom, a phosphorus atom or as in formula (II- 1) In the group shown, d represents 3; when Y ₄ is an oxygen atom or a sulfur atom, d represents 2; when Y ₄ is a single bond,

,

, -NH-CO-, -CO-NH-,

or

, d represents 2; when Y ₄ is -OY ₆ , -SY ₆ , -NY ₆ Y ₇ or -PY ₆ Y ₇ , d is 1; Y ₄ can also form a ring group with ring A, and wherein based on The amount of the polysiloxane (A) used is 100 parts by weight, the amount of the photoinitiator (C-1) represented by the formula (I) is 3 to 30 parts by weight, and the potential The antioxidant (F) is used in an amount of 0.5 to 10 parts by weight. The negative-type white photosensitive resin composition as described in claim 1, wherein the polysiloxane (A) can be obtained by performing a polycondensation reaction of a mixture, and the mixture comprises a silane monomer, and the silane monomer The body comprises a silane monomer (a-1) represented by the following formula (III-1): Si(R ₁ ) _w (OR ₂ ) _4-w (III-1) In formula (III-1), R ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbons, an alkenyl group having 2 to 10 carbons, an aryl group having 6 to 15 carbons, an alkyl group having an acid anhydride group and having 1 to 10 carbons , an alkyl group with an epoxy group and a carbon number of 1 to 10 or an alkoxy group with an epoxy group, wherein at least one R ₁ represents an alkyl group with an acid anhydride group and a carbon number of 1 to 10, an epoxy group and An alkyl group having 1 to 10 carbon atoms or an alkoxy group having an epoxy group; R ₂ independently represents a hydrogen atom, an alkyl group having a carbon number of 1 to 6, an acyl group having a carbon number of 1 to 6 or a carbon number is an aromatic group of 6 to 15; and w represents an integer of 1 to 3. The negative-type white photosensitive resin composition as described in claim 1, wherein the white pigment (E) at least comprises strontium titanate, di Titanium oxide, calcium carbonate, calcium sulfate, zinc oxide, barium sulfate, barium carbonate, silicon dioxide, aluminum powder, kaolin, clay, talc, montmorillonite, aluminum hydroxide, magnesium carbonate or white hollow polymer microspheres. The negative-type white photosensitive resin composition as described in claim 1, wherein the amount of the polysiloxane (A) used is 100 parts by weight, the compound (B) having an ethylenically unsaturated group is The usage amount is 30 to 200 parts by weight, the usage amount of the photoinitiator (C) is 3 to 45 parts by weight, the usage amount of the solvent (D) is 100 to 700 parts by weight, the white Pigment (E) is used in an amount of 70 to 600 parts by weight. A white matrix is formed by the negative-type white photosensitive resin composition as described in any one of the first to fourth claims in the scope of application. A color filter comprising a white matrix as described in claim 5 of the scope of application. A reflective display device includes a color filter as described in item 6 of the patent application scope. A white frame is formed by the negative-type white photosensitive resin composition described in any one of the first to fourth items of the patent application scope. A display device includes a white frame as described in item 8 of the patent application scope.

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