CN105022231A - Composition, thin film and method for forming the same, protective film, partition wall, and display element - Google Patents

Composition, thin film and method for forming the same, protective film, partition wall, and display element Download PDF

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CN105022231A
CN105022231A CN201510180978.5A CN201510180978A CN105022231A CN 105022231 A CN105022231 A CN 105022231A CN 201510180978 A CN201510180978 A CN 201510180978A CN 105022231 A CN105022231 A CN 105022231A
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compound
methyl
film
unsaturated group
group
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谢岦庭
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Chi Mei Corp
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Chi Mei Corp
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Abstract

The invention provides a photosensitive resin composition which can form a film with good adhesion and good hardness, a film and a forming method thereof, a protective film, a partition wall and a display element. The photosensitive resin composition comprises an alkali-soluble resin , an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a silicon atom-containing oxetane compound (D), and a solvent (E). The alkali-soluble resin includes a resin (A-1) having an ethylenically unsaturated group. The ethylenically unsaturated group-containing compound (B) includes a first ethylenically unsaturated group-containing compound (B-1), wherein the first ethylenically unsaturated group-containing compound (B-1) includes a urethane group and 7 or more acryloyl groups. The oxetane compound (D) containing a silicon atom has a weight average molecular weight of 200 to 4000.

Description

Composition, film and forming method thereof, diaphragm, dividing wall and display element
Technical field
The present invention relates to a kind of composition, film and forming method thereof, diaphragm, dividing wall and display element.The photosensitive polymer combination having the film that adherence is good and hardness is good concurrently is formed, film and forming method thereof, diaphragm, dividing wall and liquid crystal display cells in particular to a kind of.
Background technology
Generally speaking, the colour element in color filter surfaces and black matrix" can be uneven because of difference of height, and therefore the usual surface in chromatic filter layer forms diaphragm, fills and leads up uneven part by this, to reach the requirement of planarization.But, in the process manufacturing the optical element such as liquid crystal display cells or solid-state image device (solid-stateimaging device), multiple process can be stood, such as, soak the process of substrate with acid flux material or alkaline solution; Or form the process of distribution electrode layer (wiringelectrode layer) with sputter (sputtering).Above-mentioned process all can cause optical element local corrosion or produce high temperature, and therefore, diaphragm need have the characteristic can resisting these process, comprises thermotolerance, solvent resistance, acid resistance and alkali resistance etc.
On the other hand, in current color liquid crystal display device, develop dividing wall in photoetching (photolithography) mode.The mode forming dividing wall is first coated on substrate by photosensitive composite, and make photosensitive composite stand the steps such as exposure, development and be formed.In addition, the thickness that the space between cells in color liquid crystal display device can utilize photosensitive composite to be formed controls, and easily can control the accuracy of the distance in space between cells.
Because diaphragm or dividing wall are formed on colored filter or substrate, therefore high to the requirement of transparency.If the transparency of diaphragm or dividing wall is not good, when being applied to liquid crystal display cells, will the luminance shortage of liquid crystal display cells being caused, and affect the display quality of liquid crystal display cells.
For improving the transparency of diaphragm or dividing wall, Japanese Patent Laid-Open 2010-054561 patent discloses a kind of diaphragm photosensitive composite, and it includes alkali-soluble binding resin, has the compound of ethene unsaturated group, light trigger and solvent.On the other hand, Japanese Patent Laid-Open 2004-240241 patent discloses a kind of photosensitive composite, it comprises co-polymer (A), there is polymkeric substance (B) and light trigger (C) that base is closed in ethene insatiable hunger, wherein multipolymer (A) closes carboxylic acid (acid anhydride) by ethene insatiable hunger, compound and other ethene insatiable hungers of the ethene insatiable hunger conjunction base of tool epoxy radicals are closed compound institute's copolymerization of base and obtain, and light trigger (C) is 2-diacetyl-[4-methylthio phenyl]-2-(O-oxime acetate salt), 1, 2-diacetyl-1-(4-morpholino phenyl)-2-(O-benzoyl oxime), 1, 2-octadione-1-[4-thiophenyl benzene]-2-[O-(4-toluyl) oxime] or its analog.But though these photosensitive composites can obtain diaphragm or the dividing wall of high transparent, this diaphragm or dividing wall have the shortcoming that adherence is not good and hardness is not good.
Therefore, how to improve simultaneously photosensitive polymer combination form diaphragm or dividing wall adherence is not good and hardness is not good problem, to reach the requirement of current industry, desire most ardently the problem of solution for this those skilled in the art at present in fact.
Summary of the invention
In view of this, the invention provides a kind of photosensitive polymer combination for the protection of film or dividing wall, it can improve said protection film or dividing wall adherence is not good and hardness is not good problem.
The invention provides a kind of photosensitive polymer combination, it comprises: the oxetane compound (D) of alkali soluble resin (A), compound (B) containing ethene unsaturated group, light trigger (C), silicon atoms and solvent (E).Alkali soluble resin (A) comprises the resin (A-1) with ethene unsaturated group.Compound (B) containing ethene unsaturated group comprises the compound (B-1) that first contains ethene unsaturated group, wherein the first compound (B-1) containing ethene unsaturated group comprises carbamate groups (urethane group ) with 7 more than acryloyl group (acryloyl group, ).The weight average molecular weight (Mw) of the oxetane compound (D) of silicon atoms is 200 to 4000.
In one embodiment of this invention, the oxetane compound (D) of above-mentioned silicon atoms comprises the combination of the oxetane compound of the first silicon atoms, the oxetane compound of the second silicon atoms or the two.
The oxetane compound of the first silicon atoms is the compound or its condensation product that are represented by formula (1).
Si (R 1) a(OR 2) 4-aformula (1)
In formula (1), R 1and R 2respective independent represent carbon number be 1 to 8 alkyl, the carbon number naphthenic base that is 6 to 10, the carbon number aryl that is 6 to 10, carbon number be the alkyl-carbonyl of 2 to 7 or there is the organic group of oxetanylmethoxy, wherein R 1and R 2in at least one be the organic group with oxetanylmethoxy; A represents the integer being selected from 0 to 3
The oxetane compound of the second silicon atoms is that the compound represented by formula (2) reacts through heat condensation, carries out ester exchange reaction and obtain with the oxetane compound of the hydroxyl represented by formula (3).
Si (R 3) b(OR 4) 4-bformula (2)
In formula (2), R 3respective independent represent carbon number be 1 to 8 alkyl, carbon number be 6 to 10 naphthenic base or carbon number be the aryl of 6 to 10; R 4respective independent represent carbon number be 1 to 8 alkyl, carbon number be 6 to 10 naphthenic base, carbon number be 6 to 10 aryl or carbon number be the alkyl-carbonyl of 2 to 5; B represents the integer being selected from 0 to 2,
In formula (3), R 5to R 10respective independently represent hydrogen atom, fluorine atom, carbon number be 1 to 4 alkyl, there is the alkyl or phenyl of hydroxyl, wherein, R 5to R 10in at least one be the alkyl with hydroxyl.
In one embodiment of this invention, the above-mentioned resin (A-1) with ethene unsaturated group is that the co-polymer obtained by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and (a-2) copolymerization of other unsaturated compounds reacts with the unsaturated compound (a-3) with epoxy radicals and obtains.
In one embodiment of this invention, the above-mentioned compound (B) containing ethene unsaturated group comprises the compound (B-1) that first contains ethene unsaturated group.First compound (B-1) containing ethene unsaturated group comprises the acryloyl group of carbamate groups and more than 10.
In one embodiment of this invention, use amount based on alkali soluble resin (A) is 100 weight portions, the use amount with the resin (A-1) of ethene unsaturated group is 50 weight portion to 100 weight portions, use amount containing the compound (B) of ethene unsaturated group is 50 weight portion to 300 weight portions, first use amount containing the compound (B-1) of ethene unsaturated group is 30 weight portion to 250 weight portions, the use amount of light trigger (C) is 10 weight portion to 100 weight portions, the use amount of the oxetane compound (D) of silicon atoms is 10 weight portion to 80 weight portions, and the use amount of solvent (E) is 200 weight portion to 2400 weight portions.
The present invention separately provides a kind of formation method of film, comprising: on substrate, form above-mentioned photosensitive polymer combination; And treatment step is carried out to photosensitive polymer combination, to form film.
The present invention separately provides a kind of film, and it is the formation method of the film of above and obtains.
The present invention separately provides a kind of diaphragm (protection film), and it is above-mentioned film.
The present invention separately provides a kind of dividing wall (spacer), and it is above-mentioned film.
The present invention more provides a kind of liquid crystal display cells, and it comprises above-mentioned diaphragm or above-mentioned dividing wall.
Based on above-mentioned, when photosensitive polymer combination of the present invention is for the formation of diaphragm or dividing wall, the problem that adherence is not good and hardness is not good can be improved, and then be applicable to liquid crystal display cells.
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below is described in detail below.
Embodiment
< photosensitive polymer combination >
The invention provides a kind of photosensitive polymer combination, it comprises: the oxetane compound (D) of alkali soluble resin (A), compound (B) containing ethene unsaturated group, light trigger (C), silicon atoms and solvent (E).In addition, if desired, photosensitive polymer combination more can comprise adjuvant (F).
Each composition being used for photosensitive polymer combination of the present invention will be described in detail below.
Should be noted that at this, be below represent acrylic acid and/or methacrylic acid with (methyl) acrylic acid, and represent acrylate and/or methacrylate with (methyl) acrylate; Similarly, acryloyl group and/or methacryl is represented with (methyl) acryloyl group.
Alkali soluble resin (A)
Alkali soluble resin (A) comprises the resin (A-1) with ethene unsaturated group.
In addition, alkali soluble resin (A) optionally comprises other alkali soluble resins (A-2).
There is the resin (A-1) of ethene unsaturated group
The resin (A-1) with ethene unsaturated group is that the co-polymer obtained by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and (a-2) copolymerization of other unsaturated compounds reacts with the unsaturated compound (a-3) with epoxy radicals and obtains.
In detail, the synthetic method with the resin (A-1) of ethene unsaturated group is as follows: first make unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and other unsaturated compounds (a-2) through double bond copolymerization, and form the co-polymer that side chain has carboxylic acid group, then, the co-polymer making this side chain have carboxylic acid group carries out addition reaction with the unsaturated compound (a-3) with epoxy radicals, can obtain the resin (A-1) with ethene unsaturated group.
Another synthetic method with the resin (A-1) of ethene unsaturated group is as follows: the unsaturated compound (a-3) first making other unsaturated compounds (a-2) and have an epoxy radicals is through double bond copolymerization, and form the co-polymer that side chain has epoxy radicals, then, make this side chain have the co-polymer of epoxy radicals and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and carry out addition reaction, the resin (A-1) with ethene unsaturated group can be obtained.
What have the resin (A-1) of ethene unsaturated group also has a kind of synthetic method as follows: the unsaturated compound (a-3) first making other unsaturated compounds (a-2) and have an epoxy radicals is through double bond copolymerization, and form the co-polymer that side chain has epoxy radicals, then, this side chain is had after the co-polymer of epoxy radicals and unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) carry out addition reaction, half-esterification reaction (half-esterification reaction) is carried out further with anhydrides compound, the resin (A-1) with ethene unsaturated group can be obtained.
Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1)
The concrete example of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) includes but not limited to unsaturated monocarboxylic compound, unsaturated multi-carboxylic acid compounds, the polycyclic compund with unsaturated group and a carboxylic acid group, the polycyclic compund with unsaturated group and multiple carboxylic acid group, unsaturated carboxylic acid anhydrides compound or has the polycyclic compund of unsaturated group and carboxylic acid anhydrides.
The concrete example of unsaturated monocarboxylic compound comprises (methyl) acrylic acid, butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-(methyl) acryloyloxyethyl succinate monoester (2-methacryloyloxyethyl succinate monoester), 2-(methyl) acryloyloxyethyl hexahydrobenzene dicarboxylic acid esters, 2-(methyl) acryloyloxyethyl phthalic acid ester, (such as East Asia synthesis manufactures omega-carboxy-polycaprolactone polyvalent alcohol mono acrylic ester, model is the commodity of ARONIX M-5300), or the combination of above-claimed cpd.
The concrete example of unsaturated multi-carboxylic acid compounds comprises maleic acid, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, or the combination of above-claimed cpd.
The concrete example with the polycyclic compund of unsaturated group and a carboxylic acid group comprises 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene", or the combination of above-claimed cpd.
The concrete example with the polycyclic compund of unsaturated group and multiple carboxyl comprises 5,6-dicarboxyl two ring [2.2.1] hept-2-ene".
The concrete example of unsaturated carboxylic acid anhydrides compound comprises maleic anhydride, fumaric acid anhydride, mesaconic acid acid anhydride, itaconic anhydride, citraconic anhydride, or the combination of above-claimed cpd.
The concrete example with the polycyclic compund of unsaturated group and carboxylic acid anhydrides comprises 5,6-dicarboxylic anhydride two ring [2.2.1] hept-2-ene".
Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) can be used alone or combine multiple use.
The concrete example of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) is preferably and comprises acrylic acid, methacrylic acid, 2-methacryloyloxyethyl succinate, 2-methacryl base oxethyl hexahydrobenzene dicarboxylic acid esters, maleic anhydride, or the combination of above-claimed cpd.
Other unsaturated compounds (a-2)
The concrete example of other unsaturated compounds (a-2) includes but not limited to the unsaturated compound beyond (methyl) alkyl acrylate, (methyl) acrylic acid alicyclic ester, (methyl) benzyl acrylate, unsaturated dicarboxylic ester, (methyl) hydroxyalkyl acrylate, the polyethers with (methyl) acryloyl group, distyryl compound or above-claimed cpd.
The concrete example of (methyl) alkyl acrylate comprises (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid sec-butyl ester, (methyl) acrylate tert-buthyl, or the combination of above-claimed cpd.
The concrete example of (methyl) acrylic acid alicyclic ester comprises (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methyl cyclohexyl, (methyl) acrylic acid dicyclo pentyl ester { or claim three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base (methyl) acrylate, (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid tetrahydrofuran ester, or the combination of above-claimed cpd.
The concrete example of (methyl) benzyl acrylate comprises (methyl) phenyl acrylate, benzyl methacrylate, or the combination of above-claimed cpd.
The concrete example of unsaturated dicarboxylic ester comprises diethyl maleate, DEF, diethyl itaconate, or the combination of above-claimed cpd.
The concrete example of (methyl) hydroxyalkyl acrylate comprises (methyl) 2-Hydroxy ethyl acrylate or (methyl) 2-hydroxypropyl acrylate, or the combination of above-claimed cpd.
The concrete example with the polyethers of (methyl) acryloyl group comprises polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, or the combination of above-claimed cpd.
The concrete example of styrenic comprises styrene, α-methyl styrene, m-methyl styrene, p-methylstyrene, p-methoxystyrene, or the combination of above-claimed cpd.
The concrete example of the unsaturated compound beyond above-claimed cpd comprises vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, ethene ethyl ester, 1, 3-butadiene, isoprene, 2, 3-dimethyl 1, 3-butadiene, N-N-cyclohexylmaleimide, N-phenylmaleimide, N-phenylmaleimide, N-succimide base-3-maleimidobenzoyl ester, N-succimide base-4-malimidobutanoate, N-succimide base-6-maleimidohexanoic acid ester, N-succimide base-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide, or the combination of above-claimed cpd.
Other unsaturated compounds (a-2) can be used alone or combine multiple use.
Other unsaturated compounds (a-2) are preferably and comprise (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylate tert-buthyl, (methyl) benzyl acrylate, (methyl) acrylic acid dicyclo pentyl ester, isobornyl methacrylate, (methyl) acrylic acid two cyclopentyloxy ethyl ester, styrene, p-methoxystyrene, butadiene, or the combination of above-claimed cpd.
There is the unsaturated compound (a-3) of epoxy radicals
The concrete example with the unsaturated compound (a-3) of epoxy radicals includes but not limited to have (methyl) acrylate compounds of epoxy radicals, the alpha-alkyl acrylate compounds with epoxy radicals or glycidyl ether compounds.
The concrete example with (methyl) acrylate compounds of epoxy radicals comprises (methyl) Glycidyl Acrylate, (methyl) acrylic acid 2-methyl polyglycidyl, (methyl) acrylic acid 3,4-epoxy butyl ester, (methyl) acrylic acid 6,7-epoxy heptyl ester, (methyl) acrylic acid 3,4-epoxy cyclohexyl, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, or the combination of above-claimed cpd.
The concrete example with the alpha-alkyl acrylate compounds of epoxy radicals comprises α-ethylacrylate polyglycidyl, α-n-pro-pyl Glycidyl Acrylate, α-n-butyl polyglycidyl, α-ethylacrylate-6,7-epoxy heptyl ester, or the combination of above-claimed cpd.
The concrete example of glycidyl ether compounds comprises o-vinyl benzene methyl glycidyl ethers (o-vinylbenzylglycidylether), m-vinyl benzene methyl glycidyl ethers (m-vinylbenzylglycidylether), p-vinyl benzene methyl glycidyl ethers (p-vinylbenzylglycidylether), or the combination of above-claimed cpd.
The unsaturated compound (a-3) with epoxy radicals can be used alone or combine multiple use.
The unsaturated compound (a-3) with epoxy radicals is preferably and comprises glytidyl methacrylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 6,7-epoxy heptyl ester, o-vinyl benzene methyl glycidyl ethers, m-vinyl benzene methyl glycidyl ethers, p-vinyl benzene methyl glycidyl ethers, or the combination of above-claimed cpd.
The synthesis with the resin (A-1) of ethene unsaturated group can be carried out under the existence of radical initiator (radicalpolymerization initiator).Radical initiator comprises azo-compound, organic peroxide, redox (redox) are polymerization initiator.The concrete example of azo-compound comprises 2,2'-azoisobutyronitrile, 2,2'-azos two (2,4-methyl pentane nitrile), 2,2'-azos two (2,4-dimethyl-4-methoxyl-valeronitrile), or the combination of above-claimed cpd.The concrete example of organic peroxide comprises benzoyl peroxide, lauroyl peroxide, or the combination of above-claimed cpd.The concrete example of redox system polymerization initiator comprises the combination etc. of organic peroxide and amine.The radical initiator that synthesis has the resin (A-1) of ethene unsaturated group is preferably 2,2'-azoisobutyronitrile.
The synthesis with the resin (A-1) of ethene unsaturated group can be carried out in the presence of the solvent, and wherein the concrete example of solvent is identical with the concrete example of following solvents (E), does not repeat separately at this.The preferred solvents that synthesis has the resin (A-1) of ethene unsaturated group is propylene glycol monomethyl ether acetate.
When the resin (A-1) with ethene unsaturated group first makes unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and other unsaturated compounds (a-2) through double bond copolymerization, and form the co-polymer that side chain has carboxylic acid group, then, when the co-polymer making this side chain have carboxylic acid group carries out addition reaction with the unsaturated compound (a-3) with epoxy radicals and obtains, total use amount based on unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and other unsaturated compounds (a-2) is 100 weight portions, the use amount of unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) is 5 weight portion to 60 weight portions, be preferably 10 weight portion to 55 weight portions, and be more preferred from 15 weight portion to 50 weight portions, the use amount of other unsaturated compounds (a-2) is 40 weight portion to 95 weight portions, is preferably 45 weight portion to 90 weight portions, and is more preferred from 50 weight portion to 85 weight portions.In addition, total use amount based on unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and other unsaturated compounds (a-2) is 100 weight portions, the use amount with the unsaturated compound (a-3) of epoxy radicals is 10 weight portion to 40 weight portions, be preferably 12 weight portion to 35 weight portions, and be more preferred from 15 weight portion to 30 weight portions.
Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount with the resin (A-1) of ethene unsaturated group can be 50 weight portion to 100 weight portions, be preferably 60 weight portion to 100 weight portions, and be more preferred from 70 weight portion to 100 weight portions.
If have alkali soluble resin (A) not containing when having resin (A-1) of ethene unsaturated group, the film hardness that photosensitive polymer combination is formed is not good.
Other alkali soluble resins (A-2)
Except the resin (A-1) with ethene unsaturated group, alkali soluble resin (A) optionally comprises other alkali soluble resins (A-2).
Other alkali soluble resins (A-2) include but not limited to the resin with carboxylic acid group or hydroxyl.It is the resin such as resin or novolaks (novolac) resin that the concrete example of other alkali soluble resins (A-2) comprises acrylic resin, the carbamate (urethane) without ethene unsaturated group.
The acrylic resin without ethene unsaturated group can be obtained through double bond copolymerization by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1), other unsaturated compounds (a-2), also can be obtained through double bond copolymerization by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1), other unsaturated compounds (a-2) and the unsaturated compound (a-3) with epoxy radicals.。Unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1), other unsaturated compounds (a-2) and to have the concrete example of concrete example and the unsaturated carboxylic acid that the aforementioned resin (A-1) with ethene unsaturated group uses of unsaturated compound (a-3) of epoxy radicals or unsaturated carboxylic acid anhydrides compound (a-1), other unsaturated compounds (a-2) and the unsaturated compound (a-3) with epoxy radicals identical, separately do not repeat at this.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of other alkali soluble resins (A-2) can be 0 weight portion to 50 weight portion, is preferably 0 weight portion to 40 weight portion, and is more preferred from 0 weight portion to 30 weight portion.
Containing the compound (B) of ethene unsaturated group
Compound (B) containing ethene unsaturated group comprises the compound (B-1) that first contains ethene unsaturated group.
First containing the compound (B-1) of ethene unsaturated group
First compound (B-1) containing ethene unsaturated group comprises the acryloyl group of carbamate groups and more than 7, and is preferably the acryloyl group comprising carbamate groups and more than 10.
First preparation method containing the compound (B-1) of ethene unsaturated group obtains through condensation reaction such as but not limited to polyisocyanate compound and polyol compound; at least one wherein in polyisocyanate compound and polyol compound contains acryloyl group; and the sum of polyisocyanate compound and the acryloyl group contained by polyol compound is preferably more than 7, be more preferred from more than 10.First concrete example containing the commercial goods of the compound (B-1) of ethene unsaturated group comprises UV1700B (weight average molecular weight 2000 has 10 acryloyl groups), UV6300B (having 7 acryloyl groups) or the UV7640B (having 7 acryloyl groups) of the manufacture of Japanese synthetic chemical industry incorporated company; The DPHA40H (weight average molecular weight 7000 has 10 acryloyl groups) that chemical drug incorporated company of Japan manufactures or UX5001T (there are 8 acryloyl groups); UN3320HS (the weight average molecular weight 5000 that Gen Shang Industries, Inc manufactures, there are 15 acryloyl groups), UN904 (weight average molecular weight 4900, there are 10 acryloyl groups), UN3320HC (weight average molecular weight 1500 has 10 acryloyl groups); Or U15HA (weight average molecular weight 2000 has 15 acryloyl groups), UA-33H (there are 9 acryloyl groups) that chemical company of Xin Zhong village manufactures or UA-53H (there are 15 acryloyl groups).First commercial goods containing the compound (B-1) of ethene unsaturated group is preferably UV6300B, UX5001T, DPHA40H, UN3320HS, and the combination of above-mentioned commercial goods.
First compound (B-1) containing ethene unsaturated group can be used alone or combine multiple use.
When photosensitive polymer combination does not contain compound (B-1) of ethene unsaturated group containing first, the hardness of the film that photosensitive polymer combination is formed is not good.
When the compound (B-1) that first contains ethene unsaturated group has acryloyl group and the carbamate groups of more than 10, the hardness of the film that photosensitive polymer combination is formed is better.
Use amount based on alkali soluble resin (A) is 100 weight portions, first use amount containing the compound (B-1) of ethene unsaturated group can be 30 weight portion to 250 weight portions, be preferably 35 weight portion to 230 weight portions, and be more preferred from 40 weight portion to 210 weight portions.
Second containing the compound (B-2) of ethene unsaturated group
Second is first containing the compound with ethene unsaturated group beyond the compound (B-1) of ethene unsaturated group containing the concrete example of compound (B-2) of ethene unsaturated group.
The concrete example with the compound of ethene unsaturated group comprises omega-diol diacrylate, ethylene glycol dimethacrylate, BDO diacrylate, BDO dimethylacrylate, 1,6-hexanediyl ester, HDDMA, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethylacrylate, two (methyl) acrylic acid dicyclopentenyl ester, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid two (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid three (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of oxirane (being called for short EO) upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane (being called for short PO) upgrading, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, polyester two (methyl) acrylate, polyglycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate of caprolactone upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid two trihydroxy methyl propyl ester (di (trimethylolpropyl) tetra (meth) acrylate), bisphenol-A two (methyl) acrylate of ethane via epoxyethane upgrading, through bisphenol-A two (methyl) acrylate of epoxypropane upgrading, hydrogenated bisphenol A two (methyl) acrylate of ethane via epoxyethane upgrading, through hydrogenated bisphenol A two (methyl) acrylate of epoxypropane upgrading, through glycerine three (methyl) acrylate of epoxypropane upgrading, Bisphenol F two (methyl) acrylate of ethane via epoxyethane upgrading, novolaks polyglycidyl ether (methyl) acrylate, or the combination of above-claimed cpd.
Second compound (B-2) containing ethene unsaturated group can be used alone or combine multiple use.Second compound (B-2) containing ethene unsaturated group is preferably dipentaerythritol six (methyl) acrylate, dipentaerythritol four (methyl) acrylate, or the combination of above-claimed cpd.
Use amount based on alkali soluble resin (A) is 100 weight portions, use amount containing the compound (B) of ethene unsaturated group can be 50 weight portion to 300 weight portions, be preferably 55 weight portion to 280 weight portions, and be more preferred from 60 weight portion to 250 weight portions.
Light trigger (C)
The concrete example of light trigger (C) comprises oxygen-acyl group oxime compound (O-acyloxime) or other light trigger.
Oxygen-acyl group oxime compound
The concrete example of oxygen-acyl group oxime compound comprises the oxygen-acyl group oxime compound or other oxygen-acyl group oxime compound that are represented by formula (I).
Specifically, the oxygen represented by formula (I)-acyl group oxime compound is as follows.
In formula (I), X 1, X 2, X 3, X 4, X 5, X 6, X 7, X 8and X 9independently represent that hydrogen atom, halogen atom, carbon number are alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl (benzyl), benzoyl (benzoyl), the carbon number alkanoyl (alkanoyl) that is 2 to 12, carbon number be 2 to 12 alkoxy carbonyl group or the phenyloxycarbonyl of 1 to 12 separately; X 10and X 11independently represent hydrogen atom separately, be unsubstituted base replace and carbon number be 1 to 12 naphthenic base, be substituted base replace and carbon number be 1 to 12 naphthenic base, be unsubstituted base replace and carbon number be 1 to 12 straight chained alkyl, be substituted base replace and carbon number be 1 to 12 straight chained alkyl, be unsubstituted base replace and carbon number be 1 to 12 branched alkyl, be substituted base replace and carbon number be 1 to 12 branched alkyl, be unsubstituted aryl that base replaces, be substituted the aryl that base replaces, wherein substituting group comprise halogen atom, carbon number be 1 to 6 alkoxy or aryl.
The concrete example of the oxygen represented by formula (I)-acyl group oxime compound comprises 1-[4-(phenyl) phenyl]-propane-3-cyclopentane-1; 2-diketone 2-(O-benzoyl group oxime), 1-[4-(phenyl) phenyl]-heptane-1; 2-diketone 2-(O-benzoyl group oxime), 1-[4-(phenyl) phenyl]-octane-1; 2-diketone-2-(O-benzoyl group oxime), or the combination of above-claimed cpd.1-[4-(phenyl) phenyl]-octane-1; 2-diketone-2-(O-benzoyl group oxime) is manufactured by Ciba (Ciba Specialty Chemicals) company limited, and model is the commodity of IRGACUREOXE-01.
Oxygen-acyl group oxime compound can be used alone or combines multiple use.
The concrete example of other oxygen-acyl group oxime compound comprises 1-[4-(benzoyl group) phenyl]-heptane-1, 2-diketone-2-(O-benzoyl group oxime), 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone-1-(O-acetyl group oxime), 1-[9-ethyl-6-(3-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone-1-(O-acetyl group oxime), 1-[9-ethyl-6-benzoyl group-9H-carbazole-3-substituting group]-ethane ketone-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) benzoyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), or the combination of above-claimed cpd.-ethane ketone-1-(O-acetyl group oxime) can for be manufactured by Ciba company limited for 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group], and model is the commodity of IRGACURE OXE-02.
Oxygen-acyl group oxime compound can be used alone or combines multiple use.
Other oxygen-acyl group oxime compound is preferably and comprises 1-[9-ethyl-6-benzoyl group-9H-carbazole-3-substituting group]-ethane ketone-1-(O-acetyl group oxime), 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), or the combination of above-claimed cpd.
Other light trigger
The concrete example of other light trigger comprises triazine (triazine) compounds, vinylbenzene ketone (acetophenone) compounds, diimidazole (biimidazole) compounds, benzophenone (benzophenone) compounds, α-diketone (α-diketone) compounds, alcohol ketone (acyloin) compounds, alcohol ether ketone (acyloin ether) compounds, acyl phosphine oxide (acylphosphineoxide) compounds, quinone (quinone) compounds, halogen-containing compounds, superoxide (peroxide), or the combination of above-claimed cpd.
The concrete example of triazine compounds comprises vinyl-halogenated methyl-s-triazine compound (vinyl-halomethyl-s-triazine), 2-(naphtho--1-substituting group)-4, 6-bis-(halogenated methyl)-s-triazine compound (2-(naphtho-1-yl)-4, 6-di (halomethyl)-s-triazine), 4-(p-aminophenyl)-2, 6-bis-(halogenated methyl)-s-triazine compound (4-(p-aminophenyl)-2, 6-di (halomethyl)-s-triazine), or the combination of above-claimed cpd.
The concrete example of vinyl-halogenated methyl-s-triazine compound comprises 2, 4-bis-(trichloromethyl)-6-p-methoxystyrene base-s-triazine (2, 4-di (trichloromethyl)-6-(p-methoxy) styryl-s-triazine), 2, 4-bis-(trichloromethyl)-3-(the p-dimethylaminophenyl-1 of 1-, 3-butadienyl)-s-triazine (2, 4-di (trichloromethyl)-3-(1-p-dimethylaminophenyl-1, 3-butadienyl)-s-triazine], 2-trichloromethyl-3-amino-6-p-methoxystyrene base-s-triazine (2-trichloromethyl-3-amino-6-(p-methoxy) styryl-s-triazine), or the combination of above-claimed cpd.
2-(naphtho--1-substituting group)-4, the concrete example of 6-bis-(halogenated methyl)-s-triazine compound comprises 2-(naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4-methoxyl-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4-ethoxy-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4-butoxy-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-[4-(2-methoxy ethyl)-naphtho--1-substituting group]-4, 6-bis-(trichloromethyl)-s-triazine, 2-[4-(2-ethoxyethyl group)-naphtho--1-substituting group]-4, 6-bis-(trichloromethyl)-s-triazine, 2-[4-(2-butoxyethyl group)-naphtho--1-substituting group]-4, 6-bis-(trichloromethyl)-s-triazine, 2-(2-methoxyl-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(6-methoxyl-5-methyl-naphtho--2-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(6-methoxyl-naphtho--2-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(5-methoxyl-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4, 7-dimethoxy-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(6-ethoxy-naphtho--2-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4, 5-dimethoxy-naphtho--1-substituting group)-4, 6-bis-(trichloromethyl)-s-triazine, or the combination of above-claimed cpd.
4-(p-aminophenyl)-2, the concrete example of 6-bis-(halogenated methyl)-s-triazine compound comprises 4-[p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-methyl-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-methyl-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-[p-N, N-bis-(phenyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-chloroethyl carbonylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-[p-N-(p-methoxyphenyl) carbonylamino phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-bromo-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-chloro-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-bromo-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-chloro-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-bromo-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-chloro-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-bromo-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-chloro-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-ethoxycarbonylmethylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 2, 4-bis-(trichloromethyl)-6-[bromo-4-[N of 3-, N-two (ethoxy carbonyl methyl) is amino] phenyl]-1, 3, 5-triazine, or the combination of above-claimed cpd.Triazine compounds can be used alone or combines multiple use.
Triazine compounds is preferably and comprises 4-[m-bromo-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2,6-bis-(trichloromethyl)-s-triazine, 2,4-bis-(trichloromethyl)-6-p-methoxystyrene base-s-triazine, or the combination of above-claimed cpd.
The concrete example of vinylbenzene ketone compounds comprises dimethylamine vinylbenzene ketone (p-dimethylaminoacetophenone), α, α '-dimethoxy azoxy vinylbenzene ketone, 2,2 '-dimethyl-2-phenyl vinylbenzene ketone, p-methoxybenzene ethane ketone, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone, 2-benzyl-2-N, N dimethylamine-1-(4-morphlinophenyl)-1-butanone, or the combination of above-claimed cpd.
Vinylbenzene ketone compounds can be used alone or combines multiple use.
2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone can for be manufactured by Ciba company limited, and model is the commodity of IRGACURE 907.2-benzyl-2-N, N dimethylamine-1-(4-morphlinophenyl)-1-butanone can for be manufactured by Ciba company limited, and model is the commodity of IRGACURE 369.
Vinylbenzene ketone compounds is preferably and comprises 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone, 2-benzyl-2-N, N dimethylamine-1-(4-morphlinophenyl)-1-butanone, or the combination of above-claimed cpd.
The concrete example of diimidazole compounds comprises 2, 2 '-bis-(o-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(ortho-fluorophenyl base)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-aminomethyl phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-ethylphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(p-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2, 2 ', 4, 4 '-tetramethoxy phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, or the combination of above-claimed cpd.
Diimidazole compounds can be used alone or combines multiple use.
Diimidazole compounds is preferably 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole.
The concrete example of benzophenone compound comprises thioxanthones (thioxanthenone), 2,4-diethyl thioxanthone, thioxanthones-4-sulfone (thioxanthenone-4-sulfoxide), benzophenone (benzophenone), 4,4 '-bis-(dimethylamine) benzophenone (4,4 '-bis (dimethylamino) benzophenone), 4,4 '-bis-(diethylamine) benzophenone 4,4 '-bis (diethylamino) benzophenone, or the combination of above-claimed cpd.Benzophenone compound can be used alone or as a mixture.Benzophenone compound is preferably 4,4 '-bis-(diethylamine) benzophenone.
The concrete example of α-cyclohexadione compounds comprises benzil (benzil), biacetyl (diacetyl), or the combination of above-claimed cpd.α-cyclohexadione compounds can be used alone or combines multiple use.
The concrete example of ketols compound comprises diphenylhydroxyethanone (benzoin).Ketols compound can be used alone or combines multiple use.
The concrete example of keto-alcohol ether compound comprises diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether), diphenylhydroxyethanone isopropyl ether (benzoin isopropylether), or the combination of above-claimed cpd.Keto-alcohol ether compound can be used alone or combines multiple use.
The concrete example of acyl phosphine oxide compounds comprises 2; 4,6-trimethylbenzene acyl group diphenyl phosphine oxide (2,4; 6-trimethylbenzoyl diphenyl phosphineoxide), two (2; 6-dimethoxy benzoyl)-2,4,4-trimethylpentyl phosphine oxide (bis (2; 6-dimethoxy-benzoyl)-2; 4,4-trimethylbenzylphosphineoxide), or the combination of above-claimed cpd.Acyl phosphine oxide compounds can be used alone or combines multiple use.
The concrete example of quinones comprises anthraquinone (anthraquinone), 1,4-naphthoquinone (Isosorbide-5-Nitrae-naphthoquinone), or the combination of above-claimed cpd.Quinones can be used alone or combines multiple use.
The concrete example of halogen-containing compounds comprises chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), three (trichloromethyl)-s-triazine (tris (trichloromethyl)-s-triazine), or the combination of above-claimed cpd.Halogen-containing compounds can be used alone or combines multiple use.
The concrete example of superoxide comprises two-tert-butyl peroxide (di-tert-butyl) peroxide)) etc.Superoxide can be used alone or combines multiple use.
Light trigger (C) is preferably and comprises 1-[4-(phenyl) phenyl]-octane-1,2-diketone-2-(O-benzoyl group oxime) (trade name OXE-01; By Ciba, company limited manufactures), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-substituting group]-1-(O-acetyl oxime) (trade name OXE-02; By Ciba, company limited manufactures), 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone (trade name IRGACURE907; By Ciba, company limited manufactures), or its combination.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of light trigger (C) can be 10 weight portion to 100 weight portions, is preferably 12 weight portion to 90 weight portions, and is more preferred from 15 weight portion to 80 weight portions.
The oxetane compound (D) of silicon atoms
The oxetane compound (D) of silicon atoms comprises the combination of the oxetane compound of the first silicon atoms, the oxetane compound of the second silicon atoms or the two.
The weight average molecular weight of the oxetane compound (D) of silicon atoms can be 200 to 4000, is preferably 200 to 3600, and is more preferred from 200 to 3200.
The oxetane compound of the first silicon atoms is the compound or its condensation product that are represented by formula (1).
Si (R 1) a(OR 2) 4-aformula (1)
In formula (1), R 1and R 2respective independent represent carbon number be 1 to 8 alkyl, the carbon number naphthenic base that is 6 to 10, the carbon number aryl that is 6 to 10, carbon number be the alkyl-carbonyl of 2 to 7 or there is the organic group of oxetanylmethoxy (oxetanyl), wherein R 1and R 2in at least one be the organic group with oxetanylmethoxy; A represents the integer being selected from 0 to 3.
The oxetane compound of the second silicon atoms is that the compound represented by formula (2) reacts (heat of condensation reaction) through heat condensation, then carries out ester exchange reaction (ester-interchangereaction) with the oxetane compound of the hydroxyl represented by formula (3) and obtain.
Si (R 3) b(OR 4) 4-bformula (2)
In formula (2), R 3respective independent represent carbon number be 1 to 8 alkyl, carbon number be 6 to 10 naphthenic base or carbon number be the aryl of 6 to 10; R 4respective independent represent carbon number be 1 to 8 alkyl, carbon number be 6 to 10 naphthenic base, carbon number be 6 to 10 aryl or carbon number be the alkyl-carbonyl of 2 to 5; B represents the integer being selected from 0 to 2,
In formula (3), R 5to R 10respective independently represent hydrogen atom, fluorine atom, carbon number be 1 to 4 alkyl, there is the alkyl or phenyl of hydroxyl, wherein, R 5to R 10in at least one be the alkyl with hydroxyl.
The concrete example of the compound represented by formula (1) comprises 3-[(3-Ethyloxetane-3-base) methoxyl] propyl trimethoxy silicane, 3-[(3-Ethyloxetane-3-base) methoxyl] propyl-triethoxysilicane, 3-[(3-Ethyloxetane-3-base) methoxyl] propyl group triacetoxysilane, 3-[(3-Ethyloxetane-3-base) methoxyl] hydroxypropyl methyl dimethoxysilane, 3-[(3-Ethyloxetane-3-base) methoxyl] hydroxypropyl methyl diethoxy silane, 3-[(3-Ethyloxetane-3-base) methoxyl] hydroxypropyl methyl diacetoxy silane, 3-[(3-Ethyloxetane-3-base) methoxyl] dimethylamine methoxylsilane, 3-[(3-Ethyloxetane-3-base) methoxyl] propyl-dimethyl Ethoxysilane, 3-[(3-Ethyloxetane-3-base) methoxyl] propyl-dimethyl acetoxylsilane, (3-Ethyloxetane-3-base) methyltrimethoxysilane, (3-Ethyloxetane-3-base) methoxyl triethoxysilane, two [(3-Ethyloxetane-3-base) methoxyl] dimethoxysilane, two [(3-Ethyloxetane-3-base) methoxyl] diethoxy silane, three [(3-Ethyloxetane-3-base) methoxyl] methoxy silane, three [(3-Ethyloxetane-3-base) methoxyl] Ethoxysilane, or the combination of above-claimed cpd.Based on the viewpoint of hydrolysis, the compound represented by formula (1) is preferably has methoxyl.
The concrete example of the compound represented by formula (2) comprises tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, methyl triacetoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyltriacetoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, or the combination of above-claimed cpd.Based on the viewpoint that the steric hindrance (steric hindrance) of ester exchange reaction is less, the compound represented by formula (2) is preferably tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, or the combination of above-claimed cpd.
Just synthesis is easy to viewpoint, the concrete example of the oxetane compound of the hydroxyl represented by formula (3) is preferably and comprises (3-methy oxetane-3-base) methyl alcohol, (3-Ethyloxetane-3-base) methyl alcohol, 2-hydroxymethyl oxetane, or the combination of above-claimed cpd.
The commercial goods of the compound represented by formula (1), such as TMSOX or TESOX (more than, Synesis Company manufactures by East Asia).The commercial goods of the condensation product of the compound represented by formula (1), such as OX-SQ, OX-SQ-H or OX-SQ-SI20 (by East Asia, Synesis Company manufactures).The commercial goods of the oxetane compound of the second silicon atoms, such as OXT-191 (Synesis Company manufactures by East Asia).Above-mentioned commercial goods can be used alone or combines multiple use.
Based on the substrate containing silicon atom and molybdenum (molybdenum) substrate, indium tin oxide (indium-tin oxide with glass substrate, silicon nitride board etc., ITO) viewpoint of the adherence of the substrate not containing silicon atom of substrate etc., the oxetane compound (D) of silicon atoms has at least one oxetanylmethoxy, be preferably the oxetanylmethoxy with more than two, be more preferred from the oxetanylmethoxy with more than four.
If when photosensitive polymer combination does not contain oxetane compound (D) of silicon atoms, the film adherence that photosensitive polymer combination is formed is not good.
Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount of the oxetane compound (D) of silicon atoms can be 10 weight portion to 80 weight portions, be preferably 12 weight portion to 75 weight portions, and be more preferred from 15 weight portion to 70 weight portions.
Solvent (E)
The concrete example of solvent (E) comprises aromatic series based compound, alcohol based compound, ether based compound, ester based compound, ketone based compound, or the combination of above-mentioned solvent.
The concrete example of aromatic series based compound comprises benzene,toluene,xylene, or the combination of above-claimed cpd.
The concrete example of alcohol based compound comprises methyl alcohol, ethanol, or the combination of above-claimed cpd.
The concrete example of ether based compound comprises ethylene glycol ether, diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, or the combination of above-claimed cpd.
The concrete example of ester based compound comprises ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, propylene glycol monopropyl ether acetate, 3-ethoxyl ethyl propionate, or the combination of above-claimed cpd.The concrete example of ketone based compound comprises MEK, acetone, or the combination of above-claimed cpd.
Solvent (E) can be used alone or combines multiple use.
Solvent (E) is preferably and comprises diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxyl ethyl propionate, or the combination of above-mentioned solvent.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of solvent (E) can be 200 weight portion to 2400 weight portions, is preferably 300 weight portion to 2000 weight portions, and is more preferred from 400 weight portion to 1600 weight portions.
Adjuvant (F)
Under the prerequisite not affecting effect of the present invention, photosensitive polymer combination optionally adds adjuvant (F) further.The concrete example of adjuvant (F) comprise beyond surfactant (surfactant), filling agent (filler), adherence promoter (adhesion promoter), crosslinking chemical (cross-linking agent), antioxidant (antioxidant), anti-coagulants (anticoagulant) or alkali soluble resin (A) other can increase the polymkeric substance of various character (as engineering properties).
Surfactant comprises by kation system surfactant, negative ion system surfactant, nonionic system surfactant, two surfactants, polysiloxane series surfactant, fluorine atom system surface active agent, or the combination of above-mentioned surfactant.
The concrete example of surfactant comprises the polyethylene oxide alkyl ethers class of polyoxyethylene lauryl ether (polyethylene oxide lauryl ether) (polyoxyethylene lauryl ether), polyoxyethylene stearylether (polyoxyethylenestearyl ether) or polyoxyethylene oleyl ether (polyoxyethylene oleyl ether) etc.; The polyoxyethylene alkyl phenyl ethers of polyoxyethylene octylphenyl ether (polyoxyethylene octyl phenyl ether) or polyoxyethylene nonylplenyl ether (polyoxyethylene nonyl phenyl ether) etc.; The polyethylene glycol di class of polyethylene glycol dilaurate (polyethylene glycol dilaurate) or polyglycol two hard acid ester (polyethylene glycol distearate) etc.; Sorbitan fatty acid ester class (sorbitan fatty acid esters); The polyesters (fatty acid-modifiedpolyesters) of fatty acid upgrading; Or the polyurethanes of tertiary amine upgrading (tertiary amine-modifiedpolyurethane).
Surfactant can be used alone or combines multiple use.
The concrete example of the commercial goods of surfactant comprises KP (being manufactured by SHIN-ETSU HANTOTAI's chemical industry), SF-8427 is (by DOW CORNING Dong Liju silica incorporated company (Dow Corning Toray Silicone Co., Ltd.) manufacture), Polyflow (being manufactured by common prosperity society oil chemical industry), F-Top (manufactures (Tochem Products Co. by get Ke Mu incorporated company, Ltd.) manufacture), Megafac (being manufactured by large Japanese ink chemical industry (DIC)), Fluorade (being manufactured by Sumitomo 3M incorporated company (Sumitomo 3M Ltd.)), Asahi Guard or Surflon (being manufactured by Asahi Glass), SINOPOL E8008 (being manufactured by Sino-Japan synthetic chemistry), F-475 (being manufactured by large Japanese ink chemical industry) or its combination.
The concrete example of filling agent comprises glass or aluminium etc.
The concrete example of adherence promoter comprises vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, 3-amine propyl-triethoxysilicane, 3-glycidylpropyl trimethoxy silane, 3-glycidylpropyl methyldiethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methylpropionyloxy propyl trimethoxy silicane, 3-mercaptopropyl trimethoxysilane, or the combination of above-claimed cpd.
The concrete example of antioxidant comprises 2,2-thiobis (4-methyl-6-tert-butylphenol) (2,2-thiobis (4-methyl-6-t-butylphenol)), 2,6-bis--tert-butyl phenol (2,6-di-t-butylphenol), or the combination of above-claimed cpd.
The concrete example of anti-coagulants comprises sodium polyacrylate (sodium polyacrylate) etc.
The concrete example of crosslinking chemical comprises japan epoxy resin company and manufactures, and model is epoxy compound or the epoxy resin of 1031S or 157S-70 etc.
Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount of the polymkeric substance beyond the filling agent in adjuvant (F), adherence promoter, antioxidant, anti-agglutinant or alkali soluble resin (A) is no more than 10 weight portions, is preferably and is no more than 6 weight portions.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of the surfactant in adjuvant (F) is no more than 6 weight portions, is preferably and is no more than 4 weight portions.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of the crosslinking chemical in adjuvant (F) is no more than 100 weight portions, is preferably and is no more than 80 weight portions.
The preparation method of photosensitive polymer combination
Be used for preparing the method for photosensitive polymer combination such as: the oxetane compound (D) of alkali soluble resin (A), compound (B) containing ethene unsaturated group, light trigger (C), silicon atoms and solvent (E) are positioned in stirrer and stir, it is made to be uniformly mixed into solution state, also adjuvant (F) can be added if desired, after giving Homogeneous phase mixing, just can obtain the photosensitive polymer combination of solution state.
Film and forming method thereof
The invention provides a kind of formation method of film, it comprises: (i) forms above-mentioned photosensitive polymer combination on substrate; And (ii) carries out treatment step to above-mentioned photosensitive polymer combination, to form film.This treatment step comprises: steps such as exposing, develop and bake afterwards.
Film of the present invention can be used as the diaphragm or clearance body that are applied to liquid crystal display cells.Certainly, film of the present invention is not limited thereto, and also can be applicable to the core or clad material etc. of such as semiconductor element or optical waveguide.
Below to form diaphragm and clearance body is described.In one embodiment; the step forming diaphragm comprises: be first formed on transparency carrier by the pixel layer be made up of red, green and blue-colored layer; again photosensitive polymer combination is coated on pixel layer, then, carry out steps such as exposing, develop and bake afterwards.In another embodiment; the step forming clearance body comprises: on the transparency carrier being formed with diaphragm and pixel layer, forms nesa coating, then coats on nesa coating by photosensitive polymer combination; then, steps such as exposing, develop and bake afterwards is carried out.In other words, if for forming diaphragm, be then photosensitive polymer combination is coated on the pixel layer on substrate; And if for forming clearance body, be then photosensitive polymer combination is coated on the nesa coating on substrate.
Certainly, diaphragm of the present invention and clearance body are not limited to be formed on pixel layer or nesa coating, and can be formed on the various elements on substrate or on substrate.Below, also the element of upper for coating photosensitive polymer combination is called " applied thing ".
Specifically, the formation method of above-mentioned clearance body or diaphragm sequentially comprises the following steps further: (a) use sense photosensitive resin composition, to form film; B () carries out patterned exposure to film; C () removes unwanted part, to form pattern by alkali development; And (d) carries out rear roasting process, to form diaphragm or clearance body.
Step (a): form film
By rubbing method or dry film method photosensitive polymer combination coated on the substrate (applied thing) defining pixel layer or nesa coating, to form film.
Substrate can be transparency carrier or transparent conductive substrate.
Transparency carrier is such as glass substrate or resin substrate, is preferably glass substrate.The concrete example of glass substrate comprises soda-lime glass or alkali-free glass.The concrete example of resin substrate comprises polyethylene terephthalate, polybutylene terepthatlate, polyethersulfone, polycarbonate or polyimide.
Transparent conductive substrate can be has tin oxide (SnO on all surfaces of transparency carrier 2) the NESA film (U.S. must big will (PPG) register of company trade mark) that formed or there is indium oxide-tin oxide (In 2o 3-SnO 2) ito film etc. that formed.
The method forming film with rubbing method is coated on applied thing by the solution of photosensitive polymer combination.The solid concentration being applied to the photosensitive polymer combination solution of rubbing method is 5wt% to 50wt%, is preferably 10wt% to 40wt%, and is more preferred from 15wt% to 35wt%.Rubbing method includes but not limited to spraying process, rolling method, spin-coating method, slot coating processes, excellent rubbing method or ink-jet application method; Be preferably spin-coating method or slot coating processes.In addition, before rubbing method, the coated face of substrate is preferably first through heating steps.
The method of film is formed for being stacked on basement membrane by the photosensitive dry film formed by photosensitive polymer combination with dry film method.Photosensitive dry film can stack and form light-sensitive surface after removing solvent.Be applied to the photosensitive polymer combination solution of dry film method solid concentration be 5wt% to 50wt%, be preferably 10wt% to 50wt%, be more preferred from 20wt% to 50wt%, You Jia is 30wt% to 50wt%.The concrete example of the basement membrane of photosensitive dry film comprises polyethylene terephthalate (PET), tygon, polypropylene, polycarbonate or Polyvinylchloride.The thickness of the basement membrane of photosensitive dry film is preferably 15 μm to 125 μm, is more preferred from 1 μm to 30 μm.
When photosensitive dry film does not use, photosensitive dry film also can be stacking and preserve with coverlay.Coverlay is better has release property (releasing property), and when not using to make photosensitive dry film, photosensitive dry film is not separated with coverlay, but when photosensitive dry film wish uses, photosensitive dry film and coverlay can delamination.The coverlay with afore-mentioned characteristics is such as silicone release is coated with or is printed on synthetic resin film formed.The concrete example of synthetic resin film comprises polyethylene terephthalate (polyethyleneterephthalate, PET) film, polypropylene film, polyethylene film, polyvinyl chloride film or polyurethane film.The thickness of coverlay is preferably about 5 μm to 30 μm.Coverlay also can be the coverlay of lamination two layers or three layers.
Be the transparent photosensitive dry film of heat pressure adhesive on transparent base film with the concrete example of the method for dry film method stacked film.
Secondly in aforesaid method, film is preferably with rubbing method manufacture, for using the manufacture of dry film method, and is preferably and carries out pre-baked process further to film.The condition of pre-baked process can be different according to composition and blending ratio, is preferably and heats 1 minute to 15 minutes at 70 DEG C to 120 DEG C.After pre-baked process, the thickness of film is preferably 0.5 μm to 10 μm; Be more preferred from 1.0 μm to 7.0 μm.
Step (b): patterned exposure
With the light shield with specific pattern, above-mentioned film is exposed.The concrete example of the radioactive ray used in exposure process can be visible ray, ultraviolet light or far red light, and the wavelength of radioactive ray is preferably 250nm to 550nm, is preferably 365nm.
When radiological dose (exposure) is when wavelength is 365nm, measure intensity of radiation with illuminometer ((Optical Associates) company manufactures, and model is the commodity of OAI model 356) and be preferably 100J/m 2to 5000J/m 2; Be more preferred from 200J/m 2to 3,000J/m 2.
Step (c): development
Unwanted part is removed, to form pattern by alkali development.
The concrete example of developer solution is inorganic base, as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, metasilicic acid acid sodium or ammonia; Fat primary amine, as ethamine or n-propylamine; Fatty primary secondary amine, as diethylamine or n-propylamine; Fat tertiary amine, as trimethylamine, diethylamine methyl, dimethylethyl amine or triethylamine; Cycloaliphatic ring uncle acid, as pyrroles, piperidines, N-methyl piperidine, N-methyl 1,8-diazabicyclo [5.4.0]-7-undecylene or 1,5-diazabicyclo [4.3.0]-5-nonene; Aryl tertiary amine, as pyridine, methylpyrimidine, lutidines or quinoline; Quaternary ammonium salt alkali compounds, as the aqueous solution of Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.Water-miscible organic solvent or surfactant, as methyl alcohol or ethanol, also can optionally make an addition in developer solution.
The method of development is such as infusion process (dipping method), impregnation method (impregnation method) or spray process (shower method).Development is preferably carries out about 10 seconds at room temperature to 180 DEG C.
The substrate defining predetermined pattern is carried out steam purge 30 seconds to 90 seconds after development, and via pressurized air or nitrogen air-dry.
Step (d): rear roasting process
With the heating arrangement such as heating plate or baking oven, rear roasting (post-bake) process is carried out, to form clearance body or diaphragm to the substrate defining predetermined pattern.Heating-up temperature is set between 100 DEG C to 250 DEG C, and the heat time is 30 minutes to 180 minutes.
Liquid crystal display cells and preparation method thereof
The present invention more provides a kind of liquid crystal display cells, and it comprises the diaphragm or dividing wall that are formed by photosensitive polymer combination of the present invention.Liquid crystal display cells of the present invention can manufacture as described below.
First, prepare two plate bases, and with the formation method of aforementioned film, a slice or two plate bases form diaphragm or dividing wall wherein.Then, two plate bases arrange alignment film further respectively.Then, between this two plate base, configure liquid crystal, and manufacture liquid crystal born of the same parents.
In order to manufacture liquid crystal born of the same parents (cell), such as following two kinds of methods can be enumerated.
First method: first, by two plate bases across clearance body (intercellular space) relative configuration, makes respective liquid crystal orienting film relative; Sealant is used the peripheral part of two plate bases to be fit together; Filling liquid crystal is injected in the gap divided by substrate surface and sealant; And close filling orifice, so can manufacture liquid crystal born of the same parents.
Second method: the method being referred to as instillation (One Drop Fill, ODF) mode.First, the predetermined position on the plate base in two plate bases forming liquid crystal orienting film, coating such as ultra-violet solidified encapsulant; LCD alignment face drips liquid crystal; Then, another plate base of fitting, makes liquid crystal orienting film relative; Then, to substrate whole irradiation ultraviolet radiation, to make sealant cures, liquid crystal born of the same parents can be manufactured by this.
When adopting above-mentioned either method, all wishing that then liquid crystal born of the same parents being heated to liquid crystal used is, after the temperature of isotropic phase, slowly cool to room temperature, removing flowing orientation during filling liquid crystal by this.
Then, by Polarizer (polarizer) of fitting on the outer surface of liquid crystal born of the same parents, namely liquid crystal display cells of the present invention can be obtained.
The concrete example of sealant comprises the epoxy resin etc. as hardening agent.
The Polarizer used outside liquid crystal born of the same parents can be enumerated to clamp with cellulose acetate (cellulose acetate) diaphragm and make the light polarizing film (polarizing film) being referred to as " H film " of the simultaneously stability iodine gained of polyvinyl alcohol (PVA) (polyvinyl alcohol) stretching orientation and the Polarizer that formed or the Polarizer that self formed of H film.
The liquid crystal that liquid crystal cells uses can be used alone or used in combination, and liquid crystal includes but not limited to diaminobenzene class liquid crystal, pyridazine (pyridazine) class liquid crystal, schiff base (shiff Base) class liquid crystal, azoxy (azoxy) class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, biphenyl (biphenyl) class liquid crystal, cyclohexylbenzene (phenylcyclohexane) class liquid crystal, ester (ester) class liquid crystal, terphenyl (terphenyl), cyclohexyl biphenyl hexane (biphenylcyclohexane) class liquid crystal, pyrimidine (pyrimidine) class liquid crystal, dioxane (dioxane) class liquid crystal, double-octane (bicyclooctane) class liquid crystal or cubane (cubane) class liquid crystal etc., and visual demand to add be such as cholesteryl chloride (cholesteryl chloride) again, Cholesteryl pelargonate (cholesteryl nonanoate), the cholesterol liquid crystal of cholesterol carbonic ester (cholesteryl carbonate) etc., or with trade name " C-15 ", chirality (chiral) agent etc. of " CB-15 " (Merck & Co., Inc.'s manufacture), or to oxygen base benzylidene-to strong dielectricity (ferroelectric) the class liquid crystal such as amino-2-methyl butyl cinnamate in the last of the ten Heavenly stems.
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
There is the synthesis example of the resin (A-1) of ethene unsaturated group
Below illustrate that the synthesis example A-1-1 with the resin (A-1) of ethene unsaturated group is to synthesis example A-1-5:
Synthesis example A-1-1
Four cervical vertebra bottles of volume 500 milliliters arrange nitrogen inlet, stirrer, condenser pipe and thermometer, and imports nitrogen.Then, in four cervical vertebra bottles, add the propylene glycol monomethyl ether acetate of 135 weight portions, and by temperature to 100 DEG C.Then, by 2 of the methacrylic acid dicyclo pentyl ester (referred to as FA-513M) of the methacrylic acid (referred to as MAA) of 50 weight portions, 10 weight portions, the benzyl methacrylate (referred to as BzMA) of 40 weight portions and 2.6 weight portions, 2'-azoisobutyronitrile is dissolved in the propylene glycol monomethyl ether acetate of 100 weight portions, to form mixed solution, and this mixed solution was dropwise instilled in four cervical vertebra bottles in 2 hours.After 5 hours in 100 DEG C of reactions, the glytidyl methacrylate (referred to as GMA) of 40 weight portions is added to and is full of in four cervical vertebra bottles of nitrogen, and temperature is risen to 110 DEG C.React after 6 hours, after devolatilization, drying, the resin (being also called the Resin A-1-1 with ethene unsaturated group below) with ethene unsaturated group of synthesis example A-1-1 can be obtained.
Synthesis example A-1-2 is to synthesis example A-1-5
Synthesis example A-1-2 to synthesis example A-1-5 be with the step identical with synthesis example A-1-1 prepare respectively there is ethene unsaturated group Resin A-1-2 to A-1-5, and its difference be in: change the kind of monomer and use amount (as shown in table 1) thereof.
Corresponding compound is called for short as follows in table 1 and table 2.
Table 1
The synthesis example of other alkali soluble resins (A-2)
Below illustrate that the synthesis example A-2-1 of other alkali soluble resins (A-2) is to synthesis example A-2-3:
Synthesis example A-2-1
Four cervical vertebra bottles of volume 500 milliliters arrange nitrogen inlet, stirrer, condenser pipe and thermometer, and imports nitrogen.Then, in four cervical vertebra bottles, add 2,2'-azoisobutyronitriles of 1 weight portion, the propylene glycol monomethyl ether acetate of 240 weight portions, the methacrylic acid (referred to as MAA) of 50 weight portions, the methacrylic acid dicyclo pentyl ester (referred to as FA-513M) of 20 weight portions, the benzyl methacrylate (referred to as BzMA) of 30 weight portions.Then, slowly stir and be warming up to 80 DEG C, make each reactant Homogeneous phase mixing and carry out polyreaction 4 hours.Then, then be warming up to 100 DEG C, and added 2 of 0.5 weight portion, 2 '-azoisobutyronitrile.Carry out polyreaction after 1 hour, after devolatilization, drying, other alkali soluble resin (being also called other alkali soluble resin A-2-1) of synthesis example A-2-1 can be obtained.
Synthesis example A-2-2
Synthesis example A-2-2 is with the step identical with synthesis example A-2-1 to prepare other alkali soluble resin A-2-2, and its difference be in: change the kind of monomer and use amount (as shown in table 2) thereof.
Synthesis example A-2-3
Four cervical vertebra bottles of volume 500 milliliters arrange nitrogen inlet, stirrer, condenser pipe and thermometer, and imports nitrogen.Then, in four cervical vertebra bottles, add 2,2'-azoisobutyronitriles of 1 weight portion, the propylene glycol monomethyl ether acetate of 240 weight portions, the methacrylic acid (referred to as MAA) of 30 weight portions, the methacrylic acid dicyclo pentyl ester (referred to as FA-513M) of 30 weight portions, the benzyl methacrylate (referred to as BzMA) of 30 weight portions, the glytidyl methacrylate (referred to as GMA) of 10 weight portions.Then, slowly stir and be warming up to 80 DEG C, make each reactant Homogeneous phase mixing and carry out polyreaction 4 hours.Then, then be warming up to 100 DEG C, and added 2 of 0.5 weight portion, 2 '-azoisobutyronitrile.Carry out polyreaction after 1 hour, after devolatilization, drying, other alkali soluble resin (being also called other alkali soluble resin A-2-3) of synthesis example A-2-3 can be obtained.
Table 2
The synthesis example of the oxetane compound (D) of silicon atoms
Below illustrate that the synthesis example D-2 of the oxetane compound (D) of silicon atoms is to synthesis example D-3:
Synthesis example D-2
At the diacetone alcohol of 80 grams (Diacetone alcohol, DAA) in, add the TMSOX (Synesis Company manufactures by East Asia) of 27.84 grams (100 milli moles mole) and the water of 0.54 gram (30.0 milli mole mole), and after stirred at ambient temperature for a moment, stir 2 hours at 60 DEG C.Afterwards, be warming up to 160 DEG C, make diacetone alcohol and methanol azeotropic, while react 6 hours.Can obtain with the solids content concn of diacetone alcohol dilution be 20 % by weight, the oxetane compound D-2 of silicon atoms that represents with following formula (6).
Synthesis example D-3
In the diacetone alcohol of 400 grams, add the Methyl silicate53A (compound represented by formula (7) of 89.41 grams (0.1 moles mole), wherein m is 7 or 8, manufactured by Colcoat company) and (3-Ethyloxetane-3-base) methyl alcohol of 209.9 grams (1.8 moles mole), and after stirred at ambient temperature for a moment, stir 2 hours at 60 DEG C.Afterwards, be warming up to 160 DEG C, make diacetone alcohol and methanol azeotropic, while react 6 hours.Can obtain with the solids content concn of diacetone alcohol dilution be 20 % by weight, the oxetane compound D-3 of silicon atoms that represents with following formula (8).In formula (8), m is 7 or 8.
The embodiment of photosensitive polymer combination and film and comparative example
Embodiment 1 to embodiment 7 and comparative example 1 to the comparative example 6 of photosensitive polymer combination and film are below described:
Embodiment 1
A. photosensitive polymer combination
By the Resin A-1-1 with ethene unsaturated group of 100 weight portions,
The UV6300B of 30 weight portions (has 7 acryloyl groups, Japan synthetic chemical industry incorporated company manufacture) (referred to as B-1-1), the dipentaerythritol acrylate (referred to as B-2-1) of 20 weight portions, 1-[4-(phenyl) phenyl]-octane-1,2-diketone-2-(O-benzoyl group oxime) (the trade name OXE-01 of 10 weight portions; By Ciba, company limited manufactures) (referred to as C-1), 10 weight portions TESOX (synthesized by East Asia and manufacture) (referred to as D-1) and 200 weight portions propylene glycol monomethyl ether acetate (referred to as E-1) in, and after stirring with swing-out stirrer (shaking type stirrer), the photosensitive polymer combination of embodiment 1 can be manufactured to obtain.Evaluated with aftermentioned each evaluation method by obtained photosensitive polymer combination, its result is as shown in table 3.
B. film forming
The photosensitive polymer combination of embodiment 1 is coated on plain glass substrate (being of a size of 100mm × 100mm × 0.7mm) in rotary coating mode, to form the film that thickness is about 6 μm.Then, by film at 90 DEG C pre-baked 2 to 3 minutes.Then, between exposure machine and film, insert light shield, and with 100mJ/cm 2ultraviolet to pre-baked film carry out patterned exposure (exposure machine model is AG500-4N, by M & R how rice science and technology (M & R Nanotechnology) manufacture).Film through exposure be impregnated in the potassium hydroxide aqueous solution 45 to 90 seconds of 0.05%, to remove the unwanted part of the above-mentioned film through exposure.Then, plain glass baseplate is cleaned with water.Finally, bake 30 minutes after film is carried out with baking oven at 235 DEG C, above can obtaining, form the glass substrate of the film of embodiment 1.Evaluated with aftermentioned each evaluation method by the film of embodiment 1, its result is as shown in table 3.
Corresponding compound is called for short as follows in table 3 and table 4.
Embodiment 2 to embodiment 7
The photosensitive polymer combination of embodiment 2 to embodiment 7 and film prepare with the step identical with embodiment 1, and its difference be in: change the composition of photosensitive polymer combination and use amount (as shown in table 3) thereof.Evaluated with aftermentioned each evaluation method by film obtained by embodiment 2 to embodiment 7, its result is as shown in table 3.
Comparative example 1 to comparative example 6
The photosensitive polymer combination of comparative example 1 to comparative example 6 and film prepare with the step identical with embodiment 1, and its difference be in: change the composition of photosensitive polymer combination and use amount (as shown in table 4) thereof.Evaluated with aftermentioned each evaluation method by film obtained by comparative example 1 to comparative example 6, its result is as shown in table 4.
Evaluation method
A. adherence
Adherence measures according to the netted lattice (cross-hatched) of the 8.5.2 in the 8.5 adherence test method(s)s of JIS K-5400-1990 to evaluate.Film above-described embodiment and comparative example obtained is slit into 100 netted lattice with pocket knife.Then, tear after sticking with adhesive tape, observe the situation that netted lattice are residual.The netted lattice quantity come off is fewer, represents that adherence is better.According under show that assessment level evaluates adherence.
Zero: 0%≤netted lattice Shuo Liang≤5% that comes off
Netted lattice Shuo Liang≤35% that △: 5% < comes off
Netted lattice Shuo Liang≤100% that ╳: 35% < comes off
B. hardness
By the film that above-described embodiment and comparative example obtain, according to the 8.4.1 pencil test (pencil scratch test) of JIS K-5400-1990, evaluate its pencil hardness.According under show that assessment level carrys out evaluation hardness.
◎: 5H≤pencil hardness
Zero: 4H≤pencil hardness < 3H
△: 3H≤pencil hardness < 2H
╳: pencil hardness < 2H
Table 3
Table 4
Evaluation result
Learnt by table 3 and table 4, compared with the film (embodiment 1 to embodiment 7) using the photosensitive polymer combination containing the resin (A-1) with ethene unsaturated group to be formed, the hardness of the film that the film (comparative example 1,2,5) using the photosensitive polymer combination not containing the resin (A-1) with ethene unsaturated group to be formed is formed is not good.
In addition; with use compared with the film (embodiment 1 to embodiment 7) that formed containing the photosensitive polymer combination of the compound (B-1) (that is there is the compound containing ethene unsaturated group of the acryloyl group of more than 7 and carbamate groups) of ethene unsaturated group containing first, the hardness of the film that the film (comparative example 3,6) using the photosensitive polymer combination not containing the compound (B-1) of ethene unsaturated group containing first to be formed is formed is not good.
In addition, compared with the film (embodiment 1 to embodiment 7) formed with the photosensitive polymer combination of the oxetane compound (D) using silicon atoms, the adherence of the film that the film (comparative example 4,5,6) using the photosensitive polymer combination of the oxetane compound (D) not containing silicon atoms to be formed is formed is not good.
Again; when the acryloyl group and carbamate groups that will there are more than 10 first containing the compound (B-1) of ethene unsaturated group for photosensitive polymer combination (embodiment 3 to embodiment 5) time, the hardness of the film that photosensitive polymer combination is formed is better.
In sum; photosensitive polymer combination of the present invention due to comprise specific alkali soluble resin as have ethene unsaturated group resin, have the acryloyl group of more than 7 and carbamate groups containing the compound of ethene unsaturated group and the oxetane compound of silicon atoms; therefore; by photosensitive polymer combination of the present invention for the formation of film as diaphragm or dividing wall time, the advantage that this film is good with adherence and hardness is good.In other words, photosensitive polymer combination of the present invention due to containing specific composition, and can solve the problem that adherence is not good and hardness is not good of known diaphragm or dividing wall, is thus applicable to liquid crystal display cells.
Although the present invention discloses as above with embodiment; so itself and be not used to limit the present invention; have in any art and usually know the knowledgeable; without departing from the spirit and scope of the present invention; when doing a little change and retouching, therefore protection scope of the present invention is when being as the criterion depending on the appended claim person of defining.

Claims (10)

1. a photosensitive polymer combination, is characterized in that, it comprises:
Alkali soluble resin (A);
Containing the compound (B) of ethene unsaturated group;
Light trigger (C);
The oxetane compound (D) of silicon atoms; And
Solvent (E);
Wherein, alkali soluble resin (A) comprises the resin (A-1) with ethene unsaturated group,
The described compound (B) containing ethene unsaturated group comprises the compound (B-1) that first contains ethene unsaturated group; described first compound (B-1) containing ethene unsaturated group comprises the acryloyl group of carbamate groups and more than 7, and the weight average molecular weight of the oxetane compound (D) of described silicon atoms is 200 to 4000.
2. photosensitive polymer combination as claimed in claim 1, wherein, the oxetane compound (D) of described silicon atoms comprises the combination of the oxetane compound of the first silicon atoms, the oxetane compound of the second silicon atoms or the two
The oxetane compound of described first silicon atoms is the compound or its condensation product that are represented by formula (1),
Si (R 1) a(OR 2) 4-aformula (1)
In formula (1), R 1and R 2respective independent represent carbon number be 1 to 8 alkyl, the carbon number naphthenic base that is 6 to 10, the carbon number aryl that is 6 to 10, carbon number be the alkyl-carbonyl of 2 to 7 or there is the organic group of oxetanylmethoxy, wherein R 1and R 2in at least one be the organic group with oxetanylmethoxy; A represents the integer being selected from 0 to 3,
The oxetane compound of described second silicon atoms is that the compound represented by formula (2) reacts through heat condensation, carries out ester exchange reaction and obtain with the oxetane compound of the hydroxyl represented by formula (3),
Si (R 3) b(OR 4) 4-bformula (2)
In formula (2), R 3respective independent represent carbon number be 1 to 8 alkyl, carbon number be 6 to 10 naphthenic base or carbon number be the aryl of 6 to 10; R 4respective independent represent carbon number be 1 to 8 alkyl, carbon number be 6 to 10 naphthenic base, carbon number be 6 to 10 aryl or carbon number be the alkyl-carbonyl of 2 to 5; B represents the integer being selected from 0 to 2,
In formula (3), R 5to R 10respective independently represent hydrogen atom, fluorine atom, carbon number be 1 to 4 alkyl, there is the alkyl or phenyl of hydroxyl, wherein, R 5to R 10in at least one be the alkyl with hydroxyl.
3. photosensitive polymer combination as claimed in claim 1, wherein, the resin (A-1) described in ethene unsaturated group is that the co-polymer obtained by unsaturated carboxylic acid or unsaturated carboxylic acid anhydrides compound (a-1) and (a-2) copolymerization of other unsaturated compounds reacts with the unsaturated compound (a-3) with epoxy radicals and obtains.
4. photosensitive polymer combination as claimed in claim 1; wherein; the described compound (B) containing ethene unsaturated group comprises the compound (B-1) that first contains ethene unsaturated group, and the described first compound (B-1) containing ethene unsaturated group comprises the acryloyl group of carbamate groups and more than 10.
5. photosensitive polymer combination as claimed in claim 1, wherein, use amount based on described alkali soluble resin (A) is 100 weight portions, the described use amount with the resin (A-1) of ethene unsaturated group is 50 weight portion to 100 weight portions, the use amount of the described compound (B) containing ethene unsaturated group is 50 weight portion to 300 weight portions, described first use amount containing the compound (B-1) of ethene unsaturated group is 30 weight portion to 250 weight portions, the use amount of described light trigger (C) is 10 weight portion to 100 weight portions, the use amount of the oxetane compound (D) of described silicon atoms is 10 weight portion to 80 weight portions, and the use amount of described solvent (E) is 200 weight portion to 2400 weight portions.
6. a formation method for film, is characterized in that, comprising:
On substrate, form a photosensitive polymer combination, described photosensitive polymer combination is according to any one of Claims 1 to 5; And
Treatment step is carried out to described photosensitive polymer combination, to form film.
7. a film, is characterized in that, it obtains by the formation method of film as claimed in claim 6.
8. a diaphragm, is characterized in that, it is film as claimed in claim 7.
9. a dividing wall, is characterized in that, it is film as claimed in claim 7.
10. a liquid crystal display cells, is characterized in that, it comprises diaphragm as claimed in claim 8 or dividing wall as claimed in claim 9.
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