CN102955360A - Photosensitive composition, method for manufacturing molded article, molded article and semiconductor device - Google Patents
Photosensitive composition, method for manufacturing molded article, molded article and semiconductor device Download PDFInfo
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- CN102955360A CN102955360A CN2012102460301A CN201210246030A CN102955360A CN 102955360 A CN102955360 A CN 102955360A CN 2012102460301 A CN2012102460301 A CN 2012102460301A CN 201210246030 A CN201210246030 A CN 201210246030A CN 102955360 A CN102955360 A CN 102955360A
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Abstract
The present invention provides a photosensitive composition of heat resistant molded article with stability and high UV hardenability, a method for manufacturing molded article, a molded article and a semiconductor device. The method for manufacturing a molded article includes applying a photosensitive composition to at least one of a first plate and a second plate to form a coated film. The first plate is pressed against the second plate with the coated film therebetween. The coated film of the photosensitive composition is exposed. The first plate is separated from the second plate. The exposed coated film is heated. At least one of the first plate and the second plate has a pattern including concave and convex on its surface, and the coated film conforms to the pattern in the step of pressing the first plate against the second plate. The photosensitive composition includes a thioether compound, a photopolymerization initiator other than a phosphine oxide compound and an [alpha]-aminoalkylphenone compound, and a compound having 1 to 6 (meth)acryloyl groups in one molecule.
Description
Technical field
The present invention relates to a kind of photosensitive compoistion, use the manufacture method of the molding of this photosensitive compoistion, by the manufacture method of this molding gained molding and comprise the semiconductor device of this molding.
Background technology
Adding antioxidant in photosensitive compoistion can be effectively to giving thermotolerance by the molding of photosensitive compoistion gained.
Yet, have the free radical capture ability height of the antioxidant of hindered phenol structure, so have the problem of the UV hardening reduction of photosensitive compoistion.In order to improve the UV hardening, known have the method for adding the high radical initiator of hardening, but the high radical initiator of hardening has until therefore the absorption of visible region exists the low problem of storage stability.And there are the problems such as xanthochromia owing to heat in the molding that hardens, and therefore is not suitable for the transparent material purposes such as hyaline membrane or camera lens module.
On the other hand, when use contains the situation of antioxidant of sulphur, although it is little to hinder the effect of UV sclerosis, there is the deliquescent problem with respect to (methyl) acrylate compounds.Therefore, in order to improve the dissolubility with respect to (methyl) acrylate compounds, for example proposed to have in end the polymkeric substance (patent documentation 1) of sulfo-(methyl) acrylate end.And, the hardening resin composition (patent documentation 1) that contains this polymkeric substance, (methyl) acrylate compounds, reaches radical polymerization initiator has been proposed.
The prior art document
Patent documentation
Summary of the invention
The object of the present invention is to provide a kind of storage stability and UV hardening excellence and can form the photosensitive compoistion with stable on heating molding, use the manufacture method of the molding of this photosensitive compoistion, the molding of gained by the manufacture method of this molding, and the semiconductor device that comprises this molding.
The present inventor has carried out with keen determination research in order to solve above-mentioned problem; found that the manufacture method of utilizing photosensitive compoistion (described photosensitive compoistion comprises specific sulfide compound, specific Photoepolymerizationinitiater initiater, reaches the compound that specifically has (methyl) acryloyl group), using the molding of this photosensitive compoistion; the purpose of attainable cost invention, thus the present invention finished.
That is, the invention provides following [1]～[13].
[1] a kind of manufacture method of molding, it comprises following steps: the upper coating of at least either party photosensitive compoistion in the 1st plate and the 2nd plate forms the step that photosensitive compoistion is filmed; Jie films and step that described the 1st plate and described the 2nd plate are pressed every described photosensitive compoistion; Film and press under the state of described the 1st plate and described the 2nd plate every described photosensitive compoistion in being situated between, the step that described photosensitive compoistion is filmed and exposed; The step that described the 1st plate is separated with described the 2nd plate; To the described photosensitive compoistion step of filming and heating after the exposure; At least the either party of described the 1st plate and described the 2nd plate has in its surface and comprises recess and protuberance or recess, protuberance and smooth pattern, in the step that described the 1st plate and described the 2nd plate are pressed, described photosensitive compoistion is filmed and is followed described pattern
It is characterized in that: described photosensitive compoistion comprise the represented sulfide compound of (a) following general formula (1),
[changing 1]
In above-mentioned general formula (1), R
1And R
2Independence is 1～20 organic group for carbon number respectively
(b) Photoepolymerizationinitiater initiater (wherein, except phosphine oxide compound and α-amine alkyl phenones compound),
(c) in 1 molecule, has the compound of 1～6 (methyl) acryloyl groups.
[2] according to the manufacture method of above-mentioned [1] described molding, it is characterized in that:
Described (a) composition is the R of described general formula (1)
1And R
2But represent independently respectively hydrogen atom also the carbon number that replaces of alkoxy or aryloxy group be the sulfide compound of 12～18 alkyl.
[3] according to the manufacture method of above-mentioned [2] described molding, it is characterized in that:
Described (a) composition is thio-2 acid two (tridecyl) ester.
[4] according to the manufacture method of each described molding in above-mentioned [1]～[3], it is characterized in that:
Described (b) composition is the hydroxyacetone compounds with the represented base of following general formula (2);
[changing 2]
In above-mentioned general formula (2), R
4And R
5Can independently be respectively that hydrogen atom or carbon number are 1～20 organic group, R
4And R
5Also can form and have the organic group that carbon number is 3～20 ring texture.
[5] according to the manufacture method of each described molding in above-mentioned [1]～[4], it is characterized in that:
In with (a) composition and (b) composition when (c) total amount of composition is made as the situation of 100 mass parts, described (c) composition comprises (methyl) acrylate compounds that contains the aromatic series base of 10 mass parts～99.89 mass parts.
[6] according to the manufacture method of each described molding in above-mentioned [1]～[5], it is characterized in that:
In with (a) composition and (b) composition when (c) total amount of composition is made as the situation of 100 mass parts, described (c) composition comprises the represented fluorene compound of (c-1) following general formula (3) of 10 mass parts～70 mass parts;
[changing 3]
In above-mentioned general formula (3), R
6And R
7Be 2～4 straight chain shape or the alkylidene that props up chain for carbon number independently respectively; R
8And R
9Independent respectively is hydrogen atom or methyl; A and b are integer, and a+b=0～24; It is 1～28 substituting group that fluorene skeleton in the general formula (3) also can have carbon number.
[7] according to the manufacture method of each described molding in above-mentioned [1]～[6], it is characterized in that:
In with (a) composition and (b) composition when (c) total amount of composition is made as the situation of 100 mass parts, described (c) composition comprises the represented biphenol compound of (c-2) following general formula (4) of 10 mass parts～50 mass parts;
[changing 4]
In above-mentioned general formula (4), R
10Be hydrogen atom or methyl; C is 0～24 integer; It is 1～28 substituting group that biphenyl backbone in the general formula (4) also can have carbon number.
[8] according to the manufacture method of each described molding in above-mentioned [1]～[7], it is characterized in that:
Comprise described (a) composition 0.01 mass parts～20 mass parts, described (b) composition 0.1 mass parts～20 mass parts, and described (c) composition 60 mass parts～99.89 mass parts (wherein, (a) composition and (b) composition are 100 mass parts with (c) total amount of composition).
[9] according to the manufacture method of each described molding in above-mentioned [1]～[8], it is characterized in that:
Described molding is lens.
[10] a kind of molding is characterized in that:
Utilization obtains according to each described manufacture method in above-mentioned [1]～[9].
[11] a kind of molding is characterized in that:
Contain the represented sulfide compound of following general formula (1),
[changing 5]
In above-mentioned general formula (1), R
1And R
2Independence is 1～20 organic group for carbon number respectively.
[12] a kind of semiconductor device is characterized in that:
Comprise according to above-mentioned [10] or [11] described molding.
[13] a kind of photosensitive compoistion is characterized in that comprising:
(a) the represented sulfide compound of following general formula (1),
[changing 6]
In above-mentioned general formula (1), R
1And R
2Independence is 1～20 organic group for carbon number respectively
(b) Photoepolymerizationinitiater initiater (wherein, except phosphine oxide compound and α-amine alkyl phenones compound), and
(c) in 1 molecule, has the compound of 1～6 (methyl) acryloyl groups.
The effect of invention
The storage stability of photosensitive compoistion of the present invention and UV hardening are excellent.In addition, have excellent thermotolerance by the molding of photosensitive compoistion gained of the present invention, thus this molding can be used as must stable on heating material and use.
Description of drawings
Fig. 1 (a)～Fig. 1 (h) is the process flow diagram of the manufacture method of expression molding of the present invention.
Fig. 2 (a)～Fig. 2 (g) is the process flow diagram of the manufacture method of expression molding of the present invention.
The explanation of symbol:
1: the 1 plate
The face that is coated with silane coupling agent of 2: the 1 plates
3: photosensitive compoistion is filmed
4: the 2 plates
5: light
6: hardening thing
Embodiment
1. photosensitive compoistion
Photosensitive compoistion of the present invention contains (a) specific sulfide compound, (b) Photoepolymerizationinitiater initiater (wherein; except phosphine oxide compound and α-amine alkyl phenones compound), (c) have the compound of 1～6 (methyl) acryloyl groups in 1 molecule, also can optionally contain the antioxidant beyond (d) specific sulfide compound.
Below, photosensitive compoistion of the present invention is described in detail.
(a) composition
(a) composition that consists of photosensitive compoistion of the present invention is the represented sulfide compound of following general formula (1).
[changing 7]
In above-mentioned general formula (1), R
1And R
2Independence is 1～20 organic group for carbon number respectively.
Consider the R in the above-mentioned general formula (1) from the deliquescent viewpoint (methyl) acrylate compounds herein,
1And R
2Be preferably carbon number and be 12～18 alkyl, more preferably carbon number is 12～14 alkyl, is particularly preferably carbon number and is 13 alkyl.This alkyl can be the straight chain shape and props up any number of of chain.
As the concrete example of (a) composition, such as enumerating thio-2 acid two (tridecyl) ester, thiodipropionate dilauryl, thio-2 acid distearyl ester, thio-2 acid myristyl ester, thio-2 acid Lauryl Ester stearyl etc.Wherein, be preferably thio-2 acid two (tridecyl) ester.
(a) commercially available product of composition can be enumerated DLTP, DSTP, DMTP (above by Ai Biai (API CORPORATION) manufacturing), Adekastab AO-412S, AO-503 (above by the manufacturing of Ai Dike (ADEKA) incorporated company) etc.
The free radical capture ability of described (a) composition is low, does not therefore produce the problem that hardening is reduced.In addition, described (a) composition is with respect to the favorable solubility of (methyl) acrylate compounds.Therefore, the excellent storage stability of photosensitive compoistion of the present invention, the in addition molding of gained and the UV hardening is reduced and excellent heat resistance by photosensitive compoistion of the present invention.
When with (a) composition, (b) composition and (c) total amount of composition is made as 100 mass parts, (a) content of composition is preferably 0.01 mass parts～20 mass parts, more preferably 0.05 mass parts～5 mass parts are particularly preferably 0.1 mass parts～2.5 mass parts.If this quantity not sufficient 0.01 mass parts then exists stable on heating raising and inadequate phenomenon.If should amount surpass 30 mass parts, the phenomenon that then exists hardening to reduce.
(b) composition
Photosensitive compoistion of the present invention contains Photoepolymerizationinitiater initiater as (b) composition (wherein, except phosphine oxide compound and α-amine alkyl phenones compound) to give photonasty as purpose.
As the concrete example of Photoepolymerizationinitiater initiater, for example can be recited in the 365nm place and have the Photoepolymerizationinitiater initiater of putting down in writing in following (1)～(11) of absorption.
(1) benzophenone, 4,4 '-two (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4 '-benzophenone derivates such as methyldiphenyl base ketone, dibenzyl ketone, Fluorenone.
(2) 2; 2 '-diethoxy acetophenone, 2-hydroxy-2-methyl propiophenone, 2; 2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl-ketone (BASF (BASF) company makes, IRGACURE184), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propiono)-benzyl]-phenyl }-acetophenone derivs such as 2-methylpropane-1-ketone (BASF AG makes, IRGACURE127), phenyl glyoxalic acid methylester.
(3) thioxanthone derivates such as thioxanthones, 2-methyl thioxanthones, ITX, diethyl thioxanthone.
(4) benzil, benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetals, (2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl-2-methyl-propane-1-ketone) benzyl derivatives such as (BASF AG make, IRGACURE127).
(5) styrax, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenyl-propane-Benzoin derivatives such as 1-ketone.
(6) 1-phenyl-1; 2-diacetyl-2-(O-methoxycarbonyl) oxime; 1-phenyl-1; 2-propanedione-2-(O-methoxycarbonyl) oxime; 1-phenyl-1; 2-propanedione-2-(O-ethoxy carbonyl) oxime; 1-phenyl-1; 2-propanedione-2-(O-benzoyl) oxime; 1; 3-diphenylprop triketone-2-(O-ethoxy carbonyl) oxime; 1-phenyl-3-ethoxy-c triketone-2-(O-benzoyl) oxime; 1; the 2-acetyl caproyl; 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] (BASF AG makes; OXE-01); ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, (BASF AG makes 1-(O-acetyl oxime); IRGACURE OXE-02) oxime compound such as.
(7) 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propiono)-benzyl] phenyl }-the hydroxy-ketone based compounds such as 2-methylpropane.
Two cyclopentadiene titanium compounds such as (8) two (η 5-2,4-cyclopentadiene-1-yl)-two (2,6-, two fluoro-3-(1H-pyrroles-1-yl) phenyl) titanium.
(9) to benzoate derivatives such as (N, N-dimethylaminobenzoic acid) ethyl esters.
(10) acridine derivatives such as 9-phenylacridine.
(11) the polymer electrolyte Photoepolymerizationinitiater initiater such as 2-hydroxyl-1-(4-isopropenyl phenyl)-2-methylpropane-1-ketone oligomer (BASF AG makes, commodity IRGACURE907 by name).
Wherein, even the photosensitive compoistion that comprises Photoepolymerizationinitiater initiater is heated, xanthochromia is also less, considers preferred hydroxyacetone compounds from the viewpoint that does not undermine the transparency.
Hydroxyacetone compounds can be enumerated the hydroxyacetone compounds with the represented base of following general formula (2).
[changing 8]
In above-mentioned general formula (2), R
4And R
5Can independently be respectively that hydrogen atom or carbon number are 1～20 organic group, R
4And R
5Also can form and have the organic group that carbon number is 3～20 ring texture.
Hydroxyacetone compounds with the represented base of above-mentioned general formula (2) for example can be enumerated following general formula (2-1) or the represented compound of general formula (2-2).
[changing 9]
In above-mentioned general formula (2-1), R
3It is 1～20 organic group for carbon number.R
4And R
5Can independently be respectively that hydrogen atom or carbon number are 1～20 organic group, R
4And R
5Also can form and have the organic group that carbon number is 3～20 ring texture.
In above-mentioned general formula (2-2), R
4And R
5(2-1) is identical with above-mentioned general formula.R
11Be 1～20 organic group or the represented base of following general formula (2-3) for singly-bound, carbon number.
[changing 10]
In above-mentioned general formula (2-3), R
12It is 1～20 organic group for singly-bound or carbon number.
Herein, R
3Be that carbon number is 1～20 organic group, for example carbon number is saturated or undersaturated aliphatics, aromatic series or the mixing-in fat family/aromatic monovalence alkyl of 1～20 branched chain or non-branched chain.Particularly alkyl, thiazolinyl, aryl, aralkyl be can enumerate, aryl, aralkyl are preferably.R
11That singly-bound, carbon number are 1～20 organic group or the represented base of following general formula (2-3).For example can enumerate carbon number and be saturated or undersaturated aliphatics, aromatic series or the mixing-in fat family of 1～20 branched chain or non-branched chain/aromatic bivalent hydrocanbon radical, particularly be alkylidene, alkenylene, arlydene or inferior aralkyl.R
12Be that singly-bound or carbon number are 1～20 organic group, for example carbon number is 1～20 branched chain or the saturated or undersaturated aliphatic bivalent hydrocanbon radical of non-branched chain.Particularly can enumerate alkylidene, alkenylene.
Hydroxyacetone compounds with the represented base of above-mentioned general formula (2) can be recited in 1-hydroxycyclohexylphenylketone, the 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl that the 365nm place has absorption] phenyl }-2-methyl-propane-1-ketone, and the oligomer of 2-hydroxyl-1-(4-isopropenyl phenyl)-2-methylpropane-1-ketone.
Wherein, be preferably the 1-hydroxycyclohexylphenylketone, and 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl-2-methyl-propane-1-ketone.
In addition, the chemical formula of 1-hydroxycyclohexylphenylketone is shown in following formula (5).And, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl }-chemical formula of 2-methyl-propane-1-ketone is shown in following formula (6).
[changing 11]
Above-mentioned (b) composition can use separately a kind, also can will be used in combination more than 2 kinds.
When with (a) composition among the present invention, (b) composition and (c) total amount of composition is made as 100 mass parts, (b) content of composition is preferably 0.1 mass parts～20 mass parts, more preferably 0.5 mass parts～10 mass parts are particularly preferably 1 mass parts～5 mass parts.
(c) composition
Photosensitive compoistion of the present invention has the compound of 1～6 (methyl) acryloyl groups in 1 molecule by containing (c), can be owing to irradiation and described (b) composition effect and polymerization, sclerosis.
The preference of described (c) composition can be enumerated (methyl) acrylate compounds that contains the aromatic series base.
Particularly can enumerate (methyl) acrylic acid phenoxy ethyl, tribromphenol ethoxy (methyl) acrylate, (methyl) acrylate as the alcohol of the ethylene oxide adduct of phenol, as (methyl) acrylate to the alcohol of the ethylene oxide adduct of cumyl phenol, 4-(1-methyl isophthalic acid-phenylethyl) phenoxy group ethyl (methyl) acrylate, (methyl) acrylate of alcohol of ethylene oxide adduct as phenol in the ninth of the ten Heavenly Stems, 2-methacryloxyethyl phthalic acid, 2-methacryloxypropyl hexahydrophthalic acid, 2, two (2-hydroxyl-3-acryloxy propyl group phenyl) propane of 2-, oxirane is paid and is added bisphenol A-type two (methyl) acrylate, oxirane is paid and is added tetrabromobisphenol A type two (methyl) acrylate, epoxypropane is paid and is added bisphenol A-type two (methyl) acrylate, epoxypropane is paid and is added tetrabromobisphenol A type two (methyl) acrylate, bisphenol A diglycidyl ether is bisphenol type epoxy two (methyl) acrylate of gained with (methyl) acrylic acid epoxy addition reaction, the tetrabromobisphenol A diglycidyl ether is tetrabromobisphenol A type epoxy two (methyl) acrylate of gained with (methyl) acrylic acid epoxy addition reaction, the Bisphenol F diglycidyl ether is Bisphenol F type epoxy two (methyl) acrylate of gained with (methyl) acrylic acid epoxy addition reaction, tetrabromobisphenol F diglycidyl ether is tetrabromobisphenol F type epoxy two (methyl) acrylate of gained with (methyl) acrylic acid epoxy addition reaction, 2,2,2-three (methyl) acryloxy Methylethyl succinic acid, succinic acid modification pentaerythritol triacrylate etc.
In the present invention, described (c) composition preferably comprises (methyl) acrylate compounds that contains the aromatic series base of 10 mass parts～99.89 mass parts, more preferably comprises (methyl) acrylate compounds that contains the aromatic series base of 20 mass parts～95.00 mass parts.
And, consider that from the viewpoint of dissolubility, refractive index the preference that contains (methyl) acrylate compounds of aromatic series base can be enumerated the represented fluorene compound of (c-1) following general formula (3).
[changing 12]
In above-mentioned general formula (3), R
6And R
7Be 2～4 straight chain shape or the alkylidene that props up chain for carbon number independently respectively.R
8And R
9Independent respectively is hydrogen atom or methyl.A and b are integer, and a+b=0～24.It is 1～28 substituting group that fluorene skeleton in the general formula (3) also can have carbon number.
(c-1) concrete example of composition can be enumerated two [4-(2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9,9-etc.
In the present invention, described (c) composition preferably comprises (c-1) composition of 10 mass parts～70 mass parts, more preferably comprises (c-1) composition of 20 mass parts～50 mass parts.
And, consider that from the viewpoint that viscosity is adjusted the preference that contains (methyl) acrylate compounds of aromatic series base can be enumerated the represented biphenol compound of (c-2) following general formula (4).
[changing 13]
In above-mentioned general formula (4), R
10Be hydrogen atom or methyl.C is 0～24 integer.It is 1～28 substituting group that biphenyl backbone in the general formula (4) also can have carbon number.
Particularly can enumerate ethoxylation o-phenyl phenol acrylate, o-phenyl phenol glycidol ether (methyl) acrylate, hydroxyethyl o-phenyl phenol acrylate etc.
In the present invention, described (c) composition preferably comprises (c-2) composition of 10 mass parts～50 mass parts, more preferably comprises (c-2) composition of 20 mass parts～40 mass parts.
Described (c-1) composition and (c-2) (c) composition beyond the composition can enumerate following compound.
The compound that has 1 (methyl) acryloyl group in 1 molecule for example can be enumerated (methyl) isobornyl acrylate; (methyl) acrylic acid dicyclopentenyl ester; (methyl) acrylic acid two cyclopentyl esters; (methyl) acrylic acid-1-adamantane esters; (methyl) acrylic acid isodecyl ester; (methyl) acrylic acid Lauryl Ester; (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester; (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) cyclohexyl acrylate; (methyl) acrylic acid dicyclopentadienyl ester; (methyl) acrylic acid three ring decyl ester; diacetone acrylamide; isobutoxy methyl (methyl) acrylamide; NVP; the N-caprolactam; (methyl) acrylic acid-3-hydroxyl cyclohexyl; ω-carboxyl-polycaprolactone single-acrylate; 2-acryloyl group cyclohexyl succinic acid; methoxy poly (ethylene glycol) (methyl) acrylate etc.
The commercially available product that has the compound of 1 (methyl) acryloyl group in 1 molecule can be enumerated: Newfrontier IBA (the first industrial drugmaker makes); IBXA, IBXMA, ADMA (manufacturing of Osaka organic chemistry company); FA511A, FA512A, FA513A (above change into company by Hitachi make); Light ester M, E, BH, IB-X, HO-MS, HO-HH, L, PO, S, TD, Light acrylate L-A, S-A, EC-A, MTG-A, 130A, PO-A, P-200A, NP-4EA, THF-A, IB-XA, HOA-MS, HOA-MPL, HOA-MPE (above by the manufacturing of chemical company of common prosperity society); Aronix M150, M156, M5300, TO1315, TO1316 (above by the manufacturing of East Asia Synesis Company); FA544A, 512M, 512MT, 513M (above change into company by Hitachi make), NK Ester A-CMP-1E, A-LEN-10, M-450G, S, S-1800M, S-1800A, PHE-1G, NPA-8E, NPA-5P, NPA-10G, M-90G, LMA, LA, IB, CB-26, CB-23, CB-1, AMP-60G, AM-30G, A-SA, A-IB, 702A (above made by Xin Zhong village chemical industrial company) etc.
The compound that has 2 (methyl) acryloyl groups in 1 molecule for example can be enumerated ethylene glycol bisthioglycolate (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, 1; 4-butylene glycol two (methyl) acrylate, 1; 6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate etc.
The commercially available product that has the compound of 2 (methyl) acryloyl groups in 1 molecule for example can be enumerated Viscoat#700, #540 (above by the manufacturing of Osaka organic chemistry industrial group); Aronix M-208, M-210, M-215 (above by the manufacturing of East Asia Synesis Company); NK Ester A-DOD, A-NPG, DCP, A-DCP, BPE-100, BPE-200, BPE-500, A-BPE-4, A-BPEF (above by the manufacturing of Xin Zhong village chemical company); Light acrylate 1,6-HX-A, Light ester BP-4EA, BP-4PA, Epoxy ester 3002M, 3002A, 3000M, 3000A (above by the manufacturing of chemical company of common prosperity society); KAYARAD R-551, R-712 (above made by Japanese chemical drug company); BPE-4, BPE-10, BR-42M (above by the manufacturing of the first industrial drugmaker); Lipoxy VR-77, VR-60, VR-90, SP-1506, SP-1506, SP-1507, SP-1509, SP-1563 (above by clear and macromolecule company manufacturing); Neopol V779, Neopol V779MA (but above by Japanese ratio of greater inequality incorporated company (Japan U-PiCA Company, Ltd.) manufacturing) etc.
And; the compound that has 3～6 (methyl) acryloyl groups in 1 molecule for example can be enumerated three (2-hydroxyethyl) fulminuric acid ester three (methyl) acrylate; caprolactone modification three (2-hydroxyethyl) fulminuric acid ester three (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; oxirane (hereinafter referred to as " EO ") modification trimethylolpropane tris (methyl) acrylate; epoxypropane (hereinafter referred to as " PO ") modification trimethylolpropane tris (methyl) acrylate; two-trimethylolpropane four (methyl) acrylate; pentaerythrite three (methyl) acrylate; 2; 2,2-three (methyl) acryloxy Methylethyl phthalic acid; EO modification three (acryloxy) fulminuric acid ester; caprolactone modification three-(2-acryloxy ethyl) fulminuric acid ester; three (acryloxy) fulminuric acid ester; pentaerythrite four (methyl) acrylate; PO modification pentaerythrite four (methyl) acrylate; dipentaerythritol six (methyl) acrylate; dipentaerythritol five (methyl) acrylate; dipentaerythritol four (methyl) acrylate; EO modification dipentaerythritol six (methyl) acrylate; PO modification dipentaerythritol six (methyl) acrylate; caprolactone modification dipentaerythritol six (methyl) acrylate; caprolactone modification dipentaerythritol five (methyl) acrylate; two-trimethylolpropane four (methyl) acrylate; tricresyl phosphate acryloxy ethyl ester etc.
The commercially available product that has the compound of 3～6 (methyl) acryloyl groups in 1 molecule for example can be enumerated Aronix M-315, M-325, M-327, TO-756, TO-1382 (above by the manufacturing of East Asia Synesis Company); NK Ester TM-4EL, CBX-O, CBX-1N, A-DPH-6H, A-9300, A-DPH, A-9300-1CL, TMPT, TMPT-9EO, ATM-4P, ATM-4E, ATM-35E, AD-TMP, A-TMPT, A-TMPT-3EO, A-TMPT-3PO, A-TMMT, A-TMM-3LMN (above by the manufacturing of Xin Zhong village chemical industrial company); Light ester TMP, Light acrylate TMP-A, TMP-6EO-3A, PE-3A, PE-4A, DPE-6A, BA-134, TMP-3EO-A (above by the chemistry manufacturing of common prosperity society); Viscoat 295,360,3PA, 400 (above by the manufacturing of Osaka organic chemistry industrial group); KAYARAD PET-30, DPHA (above made by Japanese chemical drug company) etc.
And, also can use main chain to have polyoxyalkylene acrylate ester oligomer, polyester acrylic ester oligomer or the poly-epoxy acrylate oligomer of polyethers, polyester.
(c) composition can use separately a kind of above-claimed cpd, also can will be used in combination more than 2 kinds.
When with (a) composition, (b) composition and (c) total amount of composition is made as 100 mass parts, the content of (c) composition among the present invention is preferably 60 mass parts～99.89 mass parts, more preferably 70 mass parts～99.00 mass parts are particularly preferably 80 mass parts～98.00 mass parts.
(d) composition
In photosensitive compoistion of the present invention, can control the indurative purpose of UV and contain specific sulfide compound ((a) composition) antioxidant ((d) composition) in addition.
Described (d) composition is such as enumerating hydrazides class, hindered amine antioxidant, nitrogen heterocyclic ring sulfhydryl compound, hindered phenol antioxidant, Vitamin C acids, zinc sulfate, thiocyanic acid salt, thiourea derivative, carbohydrate, nitrite, sulphite, thiosulfate, hydroxylamine derivative etc.
In those compounds, (methyl) acrylate compounds that contains the aromatic series base in described (c-1) composition or described (c-2) are become to grade is during as the situation of (c) composition, consider preferred hindered phenol antioxidant from the viewpoint of the indurative control of UV that can carry out well photosensitive compoistion.
Described hindered phenol antioxidant for example can enumerate 3, two [2-[3-(the 3-the tributyl-4-hydroxy-5-methyl base phenyl) propionyloxies]-1 of 9-, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane, [3-(3 for pentaerythrite four, 5-2 the tributyls-4-hydroxy phenyl) propionic ester], [3-(3 for the sulphur di ethylene bis, 5-2 the tributyls-4-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-2 the tributyls-4-hydroxy phenyl) propionic ester], N, N '-hexane-1,6-two bases are two, and [3-(3,5-2 the tributyls-4-hydroxy phenyl) propionamide], 3,5-two (1, the 1-dimethyl ethyl)-the different monooctyl ester 2 of 4-hydroxy phenylpropionic acid, 4-dimethyl-6-(1-methyl pentadecyl) phenol, diethyl [[3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl] methyl] phosphonate ester 3,3 ', 3 "; 5; 5 '; 5 "-six the tributyls-a, a ', a " (sym-trimethyl benzene-2; 4; 6-three bases) three-paracresol; diethyl two [[[3; two (1; the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-] methyl] phosphonate ester] calcium, 4, two (hot sulfenyl the methyl)-orthoresol ethylenebis (oxygen ethene) two [3-(5-a tributyl-4-hydroxyl-tolyl) propionic esters] of 6-, hexa-methylene is two, and [3-(3,5-2 the tributyls-4-hydroxy phenyl) propionic ester], 1,3,5-three (3,5-2 the tributyls-4-hydroxybenzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, N-phenylaniline and 2,4, the resultant of reaction of 4-trimethylpentene, 2,6-, 2 the tributyls-4-(two (the hot sulfenyls)-1 of 4,6-, 3,5-triazine-2-base is amino) phenol, two (1,2,2,6,6-pentamethyl-4-piperidyl) [[two (1,1-the dimethyl ethyl)-4-hydroxy phenyls of 3,5-] methyl] butylmalonic acid ester, 1-[2-[3-(3,5-2 the tributyls-4-hydroxy phenyl) propionyloxy] ethyl]-4-[3-(3,5-2 the tributyls-4-hydroxy phenyl) propionyloxy]-2,2,6,6-tetramethyl piperidine 4-benzoyloxy-2,2,6,6-tetramethyl piperidine etc.
In those compounds, the ortho position (be selected from 2 and 6 at least 1) that is preferable over the phenol hydroxyl has the hindered phenol antioxidant of the large substituting group of size (such as tributyl, 1-methyl pentadecyl, hot sulfenyl methyl etc.).
Particularly can enumerate 2, the 2-sulfo-[diethyl is two-3-(3,5-2 the tributyls-4-hydroxy phenyl) propionic ester], 3, two [2-[3-(the 3-the tributyl-4-hydroxy-5-methyl base phenyl) propionyloxies]-1 of 9-, the 1-dimethyl ethyl]-2,4,8,10-, four oxaspiros [5.5] undecane etc.
When the content with described (a) composition was made as 100 mass parts, (d) content of composition was preferably 5 mass parts～100 mass parts, more preferably 10 mass parts～50 mass parts.
Other adjuvants
In photosensitive compoistion of the present invention, can contain phosphine oxide Photoepolymerizationinitiater initiater, α-amine alkyl phenones Photoepolymerizationinitiater initiater, photosensitizer, release agent, solvent, light stabilizer, antiaging agent, plastifier, connect airtight the various adjuvants such as promoter, thermal polymerization, colorant, inorganic particulate, elastic body particle, flow modifier, defoamer, spreading agent in the scope that does not undermine purpose of the present invention and characteristic.
Described photosensitizer together uses with described (b) composition usually.
Photosensitizer is such as enumerating triethylamine, diethylamine, N methyldiethanol amine, monoethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester etc.
The commercially available product of photosensitizer is such as enumerating Ubecryl P102,103,104,105 (above must (UCB) company be made by excellent happiness) etc.
Described phosphine oxide Photoepolymerizationinitiater initiater can enumerate two (2; 4; the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2; 4; 4-trimethyl-amyl group phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (the LUCILIN TPO that BASF AG makes) etc.
Described α-amine alkyl phenones Photoepolymerizationinitiater initiater can be enumerated 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 (IRGACURE369 that BASF AG makes), 2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone (IRGACURE907 that BASF AG makes), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl) butane-1-ketone etc.
2. the manufacture method of molding
Photosensitive compoistion of the present invention can obtain molding by irradiation light.
Make the method for molding as using photosensitive compoistion of the present invention, the manufacture method of the molding that for example can be listed below, it comprises following steps: the step that is coated with photosensitive resin composition of the present invention at least either party of the 1st plate and the 2nd plate; Jie films and step that described the 1st plate and described the 2nd plate are pressed every described photosensitive resin composition; Described photosensitive compoistion filmed expose and make the step of its sclerosis; The step that described the 1st plate is separated with described the 2nd plate; The described photosensitive compoistion step of filming and heating to sclerosis; At least the either party of described the 1st plate and described the 2nd plate has in its surface and comprises recess and protuberance or recess, protuberance and smooth pattern, in the step that described the 1st plate and described the 2nd plate are pressed, described photosensitive compoistion is filmed and is followed described tool patterned surface.
Fig. 1 (a)～Fig. 1 (h) and Fig. 2 (a)～Fig. 2 (g) is the process flow diagram of an example of the manufacture method of the expression molding that uses photosensitive compoistion of the present invention.Below, with reference to graphic and be illustrated.
Fig. 1 (c) and Fig. 2 (b) are that at least either party who is shown in the 1st plate and the 2nd plate is coated with photosensitive compoistion of the present invention and forms the step that photosensitive compoistion is filmed.Herein, at least one party of the 1st plate and the 2nd plate can see through the article of light by transparent resin etc. and form.Described transparent resin is not particularly limited, such as enumerating dimethyl silicone polymer with high transparency, cyclic olefin polymer etc.And the opposing party's plate can be formed by such as silicon substrate or glass substrate etc.
In Fig. 1 (a)～Fig. 1 (h) and Fig. 2 (a)～Fig. 2 (g), the 2nd plate (4) has in the surface and comprises recess, protuberance and smooth pattern, and the surface also can be the pattern that comprises recess and protuberance.And, the surface of the 1st plate (1) can smooth (Fig. 1 (a)～Fig. 1 (h)), also can have on the surface pattern (Fig. 2 (a)～Fig. 2 (g)) that comprises recess and protuberance, also can have on the surface and comprise recess, protuberance and smooth pattern.Generally, photosensitive compoistion is coated the face with those patterns.
The method that is coated with photosensitive compoistion of the present invention at least either party of the 1st plate and the 2nd plate is coated with method, rolling method, curtain coating, woodburytype, silk screen print method or ink-jet method etc. such as enumerating spin-coating method, infusion process, spray-on process, rod.
The step that Fig. 1 (e) and Fig. 2 (d) expression is situated between and films described the 1st plate and described the 2nd plate are pressed every described photosensitive compoistion.
In Fig. 1 (e) and Fig. 2 (d), in the mode that photosensitive compoistion is filmed (3) are held between the 1st plate (1) and the 2nd plate (4) the 1st plate (1) and the 2nd plate (4) are pressed, make therefrom photosensitive compoistion film (3) follow protuberance and the recess on the surface of the 1st plate or the 2nd plate.
To be expression with photosensitive compoistion film is held between described the 1st plate and described the 2nd plate and presses for Fig. 1 (f) and Fig. 2 (e), in this state described photosensitive compoistion filmed and expose and make the step of its sclerosis.
Kind as the light that shines, can use visible light, ultraviolet ray, infrared ray, X ray, alpha ray, β ray, gamma-rays etc., industrial versatility from light source is considered, the light that preferably has the wavelength of 200nm～450nm more preferably has the light of the ultraviolet wavelength that comprises 365nm.
Preferably take illumination as 1mW/cm
2～1,000mW/cm
2, exposure becomes 0.01mJ/cm
2～5,000mJ/cm
2, be preferably 0.1mJ/cm
2～1,000mJ/cm
2Mode carry out the irradiation of light.
The irradiation unit of light is such as for any one or two kinds of light sources that can utilize following two kinds of light sources and use catoptron, lens, optical fiber to produce light source of converging light etc.: the lamp source that high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, Metal halogen lamp, Excimer lamp etc. shine wider area simultaneously, the LASER Light Source such as pulse, continuous luminous.
Fig. 1 (g) and Fig. 2 (f) are the steps that expression makes described the 1st plate separate with described the 2nd plate.
In Fig. 1 (g), the result that the 1st plate (1) is separated with the 2nd plate (4) be the sclerosis photosensitive compoistion film (6) become the lip-deep state of the 1st plate (1) that is attached to.
As mentioned above, the either party that the photosensitive compoistion of described sclerosis is only filmed from the 1st plate or the 2nd plate separates, and forms the relief pattern that the photosensitive compoistion that comprises sclerosis is filmed on the surface of the opposing party's plate.
And in Fig. 2 (f), the photosensitive compoistion that hardens is filmed from both sides' separation of the 1st plate and the 2nd plate.Such shown in Fig. 2 (a)～Fig. 2 (g), when the both sides of described the 1st plate and described the 2nd plate have the situation that comprises recess and protuberance or recess, protuberance and smooth pattern on its surface, in the step that described the 1st plate and described the 2nd plate are pressed, described photosensitive compoistion is filmed and is followed the both sides of the described pattern that described the 1st plate and described the 2nd plate have, and can be attained at thus the molding that two masks have relief pattern.
After making the 1st plate and step that described the 2nd plate separates, the step that the plate that carries out filming with the photosensitive compoistion that is attached with sclerosis together heats or heats separately.Behind irradiation light, heat, can promote thus the sclerosis partly of hardening.Heating condition is different because of the allotment composition of photosensitive compoistion or the kind of adjuvant etc., and generally heating-up temperature is preferably 30 ℃～300 ℃, more preferably 50 ℃～200 ℃, is preferably 10 seconds heat time heating time～5 hours, more preferably 30 seconds～1 hour.
Before the step of above-mentioned coating photosensitive compoistion of the present invention, also can further be contained in the step of either party's silane-coating coupling agent of described the 1st plate or described the 2nd plate herein.By the silane-coating coupling agent, the adhesion of photosensitive compoistion and plate is improved.Photosensitive compoistion is attached on the plate by the face that is coated with silane coupling agent, forms the relief pattern that the photosensitive compoistion that comprises sclerosis is filmed in the surface of the plate that is coated with described silane coupling agent.
Herein, silane coupling agent for example can be enumerated trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.
The method of silane-coating coupling agent can be used the method identical with the aforesaid at least one party's who photosensitive compoistion is coated the 1st plate and the 2nd plate method.
3. molding
The molding of gained can be used in the sclerosis relief pattern etc. of hyaline membrane, lens (camera lens module etc.) or semiconductor device by the manufacture method of molding of the present invention.Wherein, consider from the aspect of excellent heat resistance, can be used as aptly the stable on heating moldings of special needs such as lens (camera lens module etc.).
Refractive index under 25 ℃ of this molding is preferably more than 1.60.And the Abbe number of this molding is preferably less than 30.
And molding of the present invention is characterised in that and contains the represented sulfide compound of following general formula (1).
[changing 14]
In above-mentioned general formula (1), R
1And R
2Independence is 1～20 organic group for carbon number respectively.
Above-mentioned sulfide compound in detail identical with aforesaid (a) composition.Molding of the present invention contains above-mentioned sulfide compound, becomes therefrom the molding of excellent heat resistance.In addition, the above-mentioned sulfide compound in the molding for example can pass through solid S
33(nuclear magnetic resonance spectrometry, NMR), the chromatography of ions, fluorophor x-ray analysis and confirm.
4. semiconductor device
Semiconductor device of the present invention comprises above-mentioned molding.Semiconductor device can be enumerated imaging apparatuss such as mobile phone with camera lens or Portable camera etc.
[example]
Below, to the present invention's more specific description in addition, but the present invention is not limited to those examples by example.
[use raw material]
The antioxidant of (a) of the present invention as being equivalent to composition can use raw material shown below.
(1-1) (Ai Dike (Adeka) incorporated company makes thio-2 acid two (tridecyl) ester, trade name: AO-503)
As other antioxidants, can use raw material shown below.
(1-2) 2, (BASF AG makes 2-sulfo-[diethyl two-3-(3,5-, 2 the tributyls-4-hydroxy phenyl) propionic ester], trade name: IRGANOX1035)
(1-3) 6-the tributyl-4-[3-[(2,4,8,10-, four tributyl dibenzo [d, f] [1,3,2] Delnav cycloheptane-6-yls) the oxygen base] propyl group]-(Sumitomo Chemical incorporated company makes the 2-methylphenol, trade name: SUMILIZER GP)
(1-4) two [3-(dodecyl sulfenyl) propionic acid]-2, two [[3-(dodecyl the sulfenyl)-1-oxopropyl oxygen base] methyl]-1 of 2-, (Xi Puluo (SHIPRO) changes into incorporated company's manufacturing, trade name to 3-glyceryl ester: SEENOX412S)
In (b) of the present invention composition, the Photoepolymerizationinitiater initiater that is equivalent to hydroxyacetone compounds can use raw material shown below.
(2-1) (BASF AG makes the 1-hydroxycyclohexylphenylketone, trade name: IRGACURE184)
(2-2) 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl }-(BASF AG makes 2-methyl-propane-1-ketone, trade name: IRGACURE127)
(2-3) (Lan Bidi (Lamberti) company makes the oligomer of 2-hydroxyl-1-(4-isopropenyl phenyl)-2-methylpropane-1-ketone, trade name: KIP150)
As other Photoepolymerizationinitiater initiater, can use raw material shown below.
(2-4) 2,4, (BASF AG makes 6-trimethylbenzoyl-diphenyl-phosphine oxide, trade name: LUCIRIN TPO)
(2-5) (BASF AG makes 2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone, trade name: IRGACURE907)
The compound with (methyl) acryloyl group of (c) of the present invention as being equivalent to composition can use raw material shown below.
(3-1) 9, (Xin Zhong village chemical industry incorporated company makes two [4-(the 2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9-, trade name: A-BPEF)
(3-2) (Xin Zhong village chemical industry incorporated company makes ethoxylation o-phenyl phenol acrylate, trade name: A-LEN-10)
(3-3) (Xin Zhong village chemical industry incorporated company makes pentaerythritol triacrylate, trade name: A-TMM-3LM-N)
(3-4) (organic chemistry Industries, Inc in Osaka makes, trade name: V#700) for bisphenol-A, EO addition product acrylate
Example 1
With respect to 9 of conduct (c) composition, two [4-(2-acryloyl-oxy base oxethyl) phenyl] fluorenes 31 mass parts of 9-are added ethoxylation o-phenyl phenol acrylate 32 mass parts, pentaerythritol triacrylate 3 mass parts, bisphenol-A, EO addition product acrylate 30.5 mass parts.
Further add 1-hydroxycyclohexylphenylketone 3 mass parts as (b) composition, add two propane thioic acid two (tridecyl) esters, 0.5 mass parts as (a) composition.One side with above compound all the blending person of forming be heated to 60 ℃, one side is stirred to dissolving with wave rotor etc., obtains photosensitive compoistion (J-1).Allotment is shown in Table 1.
Example 2～example 7 and comparative example 1～comparative example 6
According to the allotment shown in the table 1, similarly carry out with example 1 and obtain photosensitive compoistion (J-2)～photosensitive compoistion (J-13).[table 1]
Unit: mass parts
1-1: thio-2 acid two (tridecyl) ester
1-2:2,2-sulfo-[diethyl two-3-(3,5-, 2 the tributyls-4-hydroxy phenyl) propionic ester]
1-3:6-the tributyl-4-[3-[(2,4,8,10-, four tributyl dibenzo [d, f] [1,3,2] dioxathion cycloheptane-6-yl) the oxygen base] propyl group]-the 2-methylphenol
1-4: two [3-(dodecyl sulfenyl) propionic acid] 2, two [[3-(dodecyl the sulfenyl)-1-oxopropyl oxygen base] methyl]-1 of 2-, 3-glyceryl ester
The 2-1:1-hydroxycyclohexylphenylketone
2-2:2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl }-2-methyl-propane-1-ketone
The oligomer of 2-3:2-hydroxyl-1-(4-isopropenyl phenyl)-2-methylpropane-1-ketone
2-4:2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
2-5:2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone
3-1:9, two [4-(the 2-acryloyl-oxy base oxethyl) phenyl] fluorenes of 9-
3-2: ethoxylation o-phenyl phenol acrylate
3-3: pentaerythritol triacrylate
3-4: bisphenol-A, EO addition product acrylate
About the photosensitive compoistion (J-1) of gained～photosensitive compoistion (J-13), estimate as follows each physical property.Show the result in the table 2.
(1) mensuration of viscosity
Use viscosity meter (eastern machine industry company makes, VISCOMETER TV-10), measure the viscosity under 25 ℃ of photosensitive compoistion.Viscosity is preferably below the 4000mPaS.
(2) the indurative evaluation of UV
Use dropper and the photosensitive compoistion that on the chip glass of pyrex manufacturing, drips, under the state that loads dimethyl silicone polymer (PDMS) mould from it, use mask alignment device (MA100CC that Ka Ersushi (Karl Suss) company makes) and (11mW/cm that exposes
2@365nm)., peel off PDMS mould, with the finger touch lens surface, confirm having or not of viscosity thereafter.Change exposure and confirm having or not of viscosity, estimate the minimum exposure of the imperceptible viscosity that becomes.Minimum exposure is preferably below the 2.0J.
(3) evaluation of the cyclic hardening under the PDMS mould
Similarly carry out with the indurative evaluation of above-mentioned UV, use the PDMS mould and carry out forming lens 30 times by photosensitive compoistion, utilize the lens surface of observation by light microscope gained.Estimate the PDMS mould access times that confirm scar in the lens surface of gained.Access times are preferably more than 30 times.
(4) mensuration of refractive index and Abbe number
On demoulding poly terephthalic acid second two fat (PET) film, be coated with photosensitive compoistion, in around set the distance piece that thickness is 0.5mm after, under the state of chip glass of mounting pyrex system, use mask alignment device (MA100CC that Karl Suss company makes) and carry out 2 minutes exposure (11mW/cm
2@365nm).Be to peel off demoulding PET film and chip glass on the cured film of 500 μ m from the thickness of gained, use 150 ℃ baking oven (STPH-101 that Ace peck (ESPEC) incorporated company makes) and carry out 1 hour annealing in process.Thereafter, use multi-wavelength Abbe refractometer (love delay the DR-M2 that incorporated company makes) and measure refractive index under each wavelength of 486nm (F ray), 589nm (D ray), 656nm (C ray), according to the refractive index of 3 wavelength of gained, use v
D=(n
D-1)/(n
F-n
C) formula and obtain the Abbe number of cured film.
Refractive index under the preferred 589nm is more than 1.60, and Abbe number is below 30.
(5) mensuration of initial transmission
On demoulding PET film, be coated with photosensitive compoistion, in around set the distance piece that thickness is 0.5mm after, under the state of chip glass of mounting pyrex system, use mask alignment device (MA100CC that Karl Suss company makes) and carry out 2 minutes exposure (11mW/cm
2@365nm).Be to peel off demoulding PET film on the cured film of 500 μ m from the thickness of gained, use 150 ℃ baking oven (STPH-101 that ESPEC incorporated company makes) and carry out 1 hour annealing in process.Use spectrophotometer (the Ubest V-570 that Japanese light splitting incorporated company makes) and measure transmissivity under the wavelength 400nm.Transmissivity is preferably more than 95%.
(6) stable on heating evaluation
Obtaining thickness with above-mentioned similarly carrying out by photosensitive compoistion is the cured film of 500 μ m.On the cured film of gained, peel demoulding PET film, use 150 ℃ baking oven (ESPEC incorporated company make STPH-101) and carry out 1 hour annealing in process.Secondly, uses 260 ℃ baking oven (STPH-101 of ESPEC incorporated company manufacturing) and cured film carried out repeatedly 3 times 10 minutes reflow treatment.Use spectrophotometer (Ubest V-570 that Japanese light splitting incorporated company make) and measure transmissivity under the wavelength 400nm thereafter.Transmissivity after the heat resistant test is preferably more than 95%.
(7) evaluation of storage stability
Photosensitive compoistion is statically placed in remains 23 ℃ indoor, after 60 days so that foreign, precipitate etc. to be arranged in the Visual Confirmation liquid.And, use viscosity meter (eastern machine industry VISCOMETER TV-10) and measure viscosity 25 ℃ under, estimate and place front and back and have or not the variation of finding viscosity.To without precipitate, the unchanged situation of viscosity as " qualified ", will exist the situation of precipitate or the variation of discovery viscosity as defective.
[table 2]
Claims (13)
1. the manufacture method of a molding, it comprises following steps:
The upper coating of at least either party photosensitive compoistion in the 1st plate and the 2nd plate forms the step that photosensitive compoistion is filmed;
Jie films and step that described the 1st plate and described the 2nd plate are pressed every described photosensitive compoistion;
Film and press under the state of described the 1st plate and described the 2nd plate every described photosensitive compoistion in being situated between, the step that described photosensitive compoistion is filmed and exposed;
The step that described the 1st plate is separated with described the 2nd plate; And
To the described photosensitive compoistion step of filming and heating after the exposure;
At least the either party of described the 1st plate and described the 2nd plate has in its surface and comprises recess and protuberance or recess, protuberance and smooth pattern, in the step that described the 1st plate and described the 2nd plate are pressed, described photosensitive compoistion is filmed and is followed described pattern
It is characterized in that: described photosensitive compoistion comprise the represented sulfide compound of (a) following general formula (1),
[changing 1]
In above-mentioned general formula (1), R
1And R
2Respectively independent for carbon number be 1～20 organic group,
(b) Photoepolymerizationinitiater initiater, wherein except phosphine oxide compound and α-amine alkyl phenones compound, and
(c) in 1 molecule, has the compound of 1～6 (methyl) acryloyl groups.
2. the manufacture method of molding according to claim 1 is characterized in that:
Described (a) composition is the R of described general formula (1)
1And R
2But represent independently respectively hydrogen atom also the carbon number that replaces of alkoxy or aryloxy group be the sulfide compound of 12～18 alkyl.
3. the manufacture method of molding according to claim 2 is characterized in that:
Described (a) composition is thio-2 acid two (tridecyl) ester.
4. the manufacture method of each described molding in 3 according to claim 1 is characterized in that:
Described (b) composition is the hydroxyacetone compounds with the represented base of following general formula (2);
[changing 2]
In above-mentioned general formula (2), R
4And R
5Can independently be respectively that hydrogen atom or carbon number are 1～20 organic group, R
4And R
5Also can form and have the organic group that carbon number is 3～20 ring texture.
5. the manufacture method of each described molding in 3 according to claim 1 is characterized in that:
In with (a) composition and (b) composition when (c) total amount of composition is made as the situation of 100 mass parts, described (c) composition comprises (methyl) acrylate compounds that contains the aromatic series base of 10 mass parts～99.89 mass parts.
6. the manufacture method of each described molding in 3 according to claim 1 is characterized in that:
In with (a) composition and (b) composition when (c) total amount of composition is made as the situation of 100 mass parts, described (c) composition comprises the represented fluorene compound of (c-1) following general formula (3) of 10 mass parts～70 mass parts;
[changing 3]
In above-mentioned general formula (3), R
6And R
7Be 2～4 straight chain shape or the alkylidene that props up chain for carbon number independently respectively; R
8And R
9Independent respectively is hydrogen atom or methyl; A and b are integer, and a+b=0～24; It is 1～28 substituting group that fluorene skeleton in the general formula (3) also can have carbon number.
7. the manufacture method of each described molding in 3 according to claim 1 is characterized in that:
In with (a) composition and (b) composition when (c) total amount of composition is made as the situation of 100 mass parts, described (c) composition comprises the represented biphenol compound of (c-2) following general formula (4) of 10 mass parts～50 mass parts;
[changing 4]
In above-mentioned general formula (4), R
10Be hydrogen atom or methyl; C is 0～24 integer; It is 1～28 substituting group that biphenyl backbone in the general formula (4) also can have carbon number.
8. the manufacture method of each described molding in 3 according to claim 1 is characterized in that:
Comprise described (a) composition 0.01 mass parts～20 mass parts, described (b) composition 0.1 mass parts～20 mass parts, and described (c) composition 60 mass parts～99.89 mass parts, wherein (a) composition and (b) composition are 100 mass parts with (c) total amount of composition.
9. the manufacture method of each described molding in 3 according to claim 1 is characterized in that:
Described molding is lens.
10. molding is characterized in that:
Utilize according to claim 1 the manufacture method of each described molding in 9 and obtain.
11. a molding is characterized in that:
Contain the represented sulfide compound of following general formula (1),
[changing 5]
In above-mentioned general formula (1), R
1And R
2Independence is 1～20 organic group for carbon number respectively.
12. a semiconductor device is characterized in that:
Comprise according to claim 10 or 11 described moldings.
13. a photosensitive compoistion is characterized in that comprising:
(a) the represented sulfide compound of following general formula (1),
[changing 6]
In above-mentioned general formula (1), R
1And R
2Respectively independent for carbon number be 1～20 organic group,
(b) Photoepolymerizationinitiater initiater, wherein except phosphine oxide compound and α-amine alkyl phenones compound, and
(c) in 1 molecule, has the compound of 1～6 (methyl) acryloyl groups.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011181199 | 2011-08-23 | ||
| JP2011-181199 | 2011-08-23 | ||
| JP2012-100621 | 2012-04-26 | ||
| JP2012100621 | 2012-04-26 |
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| CN2012102460301A Pending CN102955360A (en) | 2011-08-23 | 2012-07-16 | Photosensitive composition, method for manufacturing molded article, molded article and semiconductor device |
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| Country | Link |
|---|---|
| CN (1) | CN102955360A (en) |
| TW (1) | TWI547758B (en) |
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| CN105934690A (en) * | 2014-03-31 | 2016-09-07 | 日东电工株式会社 | Resin composition for use in optical component and optical component using same |
| CN114779591A (en) * | 2022-06-23 | 2022-07-22 | 之江实验室 | Super-resolution photoetching method based on double-color double-step absorption effect |
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| JPH10207067A (en) * | 1997-01-16 | 1998-08-07 | Fuji Photo Film Co Ltd | Positive photoresist composition to be exposed to far ultraviolet rays |
| JP2002146276A (en) * | 2000-11-08 | 2002-05-22 | Nippon Kayaku Co Ltd | Protective film composition |
| JP2003131363A (en) * | 2001-10-26 | 2003-05-09 | Fuji Photo Film Co Ltd | Original plate of planographic printing plate |
| JP2004205622A (en) * | 2002-12-24 | 2004-07-22 | Konica Minolta Holdings Inc | Photosensitive composition, photosensitive lithographic printing plate material and method for forming image |
| CN101620376A (en) * | 2008-07-02 | 2010-01-06 | 富士胶片株式会社 | Curing combination for stamping, condensate using the combination and method for producing the same, and members for liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009078336A1 (en) * | 2007-12-14 | 2009-06-25 | Asahi Kasei E-Materials Corporation | Photosensitive resin composition |
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2012
- 2012-07-16 CN CN2012102460301A patent/CN102955360A/en active Pending
- 2012-07-23 TW TW101126500A patent/TWI547758B/en active
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|---|---|---|---|---|
| JPH10207067A (en) * | 1997-01-16 | 1998-08-07 | Fuji Photo Film Co Ltd | Positive photoresist composition to be exposed to far ultraviolet rays |
| JP2002146276A (en) * | 2000-11-08 | 2002-05-22 | Nippon Kayaku Co Ltd | Protective film composition |
| JP2003131363A (en) * | 2001-10-26 | 2003-05-09 | Fuji Photo Film Co Ltd | Original plate of planographic printing plate |
| JP2004205622A (en) * | 2002-12-24 | 2004-07-22 | Konica Minolta Holdings Inc | Photosensitive composition, photosensitive lithographic printing plate material and method for forming image |
| CN101620376A (en) * | 2008-07-02 | 2010-01-06 | 富士胶片株式会社 | Curing combination for stamping, condensate using the combination and method for producing the same, and members for liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105934690A (en) * | 2014-03-31 | 2016-09-07 | 日东电工株式会社 | Resin composition for use in optical component and optical component using same |
| CN114779591A (en) * | 2022-06-23 | 2022-07-22 | 之江实验室 | Super-resolution photoetching method based on double-color double-step absorption effect |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201310169A (en) | 2013-03-01 |
| TWI547758B (en) | 2016-09-01 |
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