TW201238992A - Thermosetting crosslinking cyclic olefin resin composition, thermosetting crosslinking cyclic olefin resin film, method for producing thermosetting crosslinking cyclic olefin resin composition and method for producing thermosetting crosslinking cyclic ol - Google Patents

Abstract

Thermosetting crosslinking cyclic olefin resin composition of the present invention is obtained by heating, ring opening metathesis polymerization and crosslinking polymerizable composition which contains 100 parts by weight of (a) cyclic olefin monomer, 0.7 to 40 parts by weight of (b) [except for the (a), crosslinking agent having two or more polymerizable unsaturated bonds], 1.15 to 15 parts by weight of (c) organic peroxide series thermal polymerization initiator having one minute half-life temperature of 135 to 200 DEG C, and (d) ring opening metathesis polymerization catalyst.

Description

[Technical Field] The present invention relates to a thermosetting olefin resin composition having a large water contact angle on a surface and a thermosetting hydrocarbon resin film containing the composition. The yield of the assembly step of the thin film 1C wafer including the resin composition of the present invention, the semiconductor packaging step of the LED, the laminated hot pressing step at the time of multilayer printing, and the attaching step in the production of the flexible printed wiring board is improved. Further, the method for producing the composition and the method for producing the film. [Prior Art] The use of a thin resin as a raw material of various molded articles is one of the uses of a molded article of a thin smoke resin, and the resin film is excellent in light weight, good in workability, and easy to incinerate. However, there is a disadvantage that the heat resistance is poor, and since it is used for the use of the south temperature of not more than °C, the improvement is reviewed. In the use of a resin film having high temperature heat resistance, a release film of a mechanical process. The release film is a small-sized semiconductor chip such as a thin 1C wafer or a LED for demolding a sealing material or a prepreg, and is miniaturized and thinned by a mobile device such as a mobile phone. exhibition. The shape of the package wafer in which such components are sealed also varies. In the past, the surface mount component has a chip frame in which the shape of the lead frame is not encapsulated. The chip is packaged on the component in the shape of a chip size package (CSP), 3 (BGA), and a four-sided flat wireless package. The (bfn) and other shaped cross-linked cyclic cyclic olefinic copolymers contribute to the use of a cover layer made of a wiring board. Yu. Due to the penetration point, it is widely available in 100 packages with a semi-conductive package. Thinner, more advanced. Recently, wafer layout is directly arranged. Grid array package -4- 201238992 The chip system is becoming mainstream. These shapes have points that contribute to the miniaturization of the machine. Furthermore, the packaged wafer is thin, which contributes to thinning of the sealing film thickness. However, the rupture of the product and the sealing material are reduced in the process of mounting the packaged wafer. It is reviewed by using the auxiliary film of the release film to improve the yield (for example, the polytetrapod-tetrafluoroethylene copolymer (ETFE) and the polyfluorene of the material of the release film used in the patent document method. Sub-PTFE and ETFE release film are produced; base fluorine, perfluoroisobutylene, etc., can not be incinerated when the environment is not lost. On the other hand, review the liquid material containing cyclodepolymerization and polymerization of cyclic olefins. The carrier is a release film (for example, the patent document has a small water contact angle, and does not have sufficient mold release property with the resin used for the sealing material or the semiconductor. PRIOR ART DOCUMENT Patent Document Patent Document 1 Japanese Laid-Open Patent Publication No. Publication No. Japanese Patent Laid-Open Publication No. Publication No. JP-A No. JP-A No. In the case of: easy to occur, the sealing method of manufacturing good ^, by 1 and 2). The seal L-diethyl (PTFE), ethylamine is high-priced, and I * harmful hydrogen fluoride, a few! a catalyst and a cross-linking resin which can be decomposed into a resin 3). However, the film is made of a tablet and an adhesive. 2000-167841, JP-A-2001-250838, JP-A-2001-253934-5-201238992 [Problems to be Solved by the Invention] Recently, it has been desired to provide a thermosetting crosslinked cyclic hydrocarbon resin containing a ring-opening metathesis of a cyclic (tetra) hydrocarbon monomer, which can be supplied and used together with a sealing material, a prepreg, and an adhesive. The resin has sufficient mechanical properties such as mold release property, tensile elongation at break, tensile strength at break, tensile strength, and high-temperature discoloration resistance before and after heating, and the resin composition of the film that can be incinerated at the time of disposal, but has not been found yet. The resin composition of the present invention solves the problem of providing a thermosetting crosslinked cyclic olefin resin obtained by ring-opening metathesis polymerization of a cyclic olefin monomer, and can be supplied with a sealing material and a prepreg. a film having mechanical strength, water repellency, high temperature and discoloration resistance such as mold release property, tensile elongation at break, tensile strength at break before and after heating of the resin used for the adhesive A resin composition comprising a film of the resin composition, a method for producing the composition, and a method for producing the film. [Means for Solving the Problem] The inventors of the present invention conducted a focused review and found that (a) a cyclic olefin monomer, (b) [a crosslinking agent having two or more polymerizable unsaturated bonds in addition to the (a)], and an organic peroxide-based thermal polymerization having a half-life temperature of 135 to 200 ° C A thermosetting crosslinked cyclic olefin resin composition obtained by heating, ring-opening metathesis polymerization, and crosslinking of a polymerizable composition of an initiator, which is supplied with sufficient heating with a resin used for a sealing material, a prepreg, and an adhesive. A film of a thermosetting crosslinked cyclic olefin resin of the present invention, a film formed of the resin composition, and the like, which have a mold release property before and after, a high mechanical strength, a high water repellency, and a high temperature and discoloration resistance film. Production method. -6 - 201238992 The thermosetting crosslinked cyclic olefin resin composition of the present invention contains 100 parts by mass of (a) a cyclic olefin monomer, and 0.7 to 40 parts by mass of (b) [except for (a) The cross-linking agent having two or more polymerizable unsaturated bonds], and the (c) one-minute half-life temperature of 1.15 to 15 parts by mass is 135 to 2 Torr. The organic peroxide-based thermal polymerization initiator of C and the polymerizable composition of the ring-opening metathesis polymerization catalyst are heated, ring-opened metathesis polymerization, and crosslinked. The thermosetting crosslinked cyclic olefin resin film of the present invention comprises the above composition. A preferred use of the above thermosetting crosslinked cyclic olefin resin film is a release film used in a semiconductor packaging step or a printing substrate manufacturing step. The method for producing a thermosetting crosslinked cyclic olefin resin composition of the present invention comprises: (b) containing (inclusive) (a) containing 100 parts by mass of (a) a cyclic olefin monomer, 〇 7 to 4 parts by mass Other than 'crosslinking agent having two or more polymerizable unsaturated bonds', 1.1 5 to 15 parts by mass of (c) organic peroxide-based thermal polymerization initiator having a one-minute half-life temperature of from 1 to 35 ° C And (d) a step of heating, ring-opening metathesis polymerization, and crosslinking of the polymerizable composition of the ring-opening metathesis polymerization catalyst. The method for producing a thermosetting crosslinked cyclic olefin resin film of the present invention comprises: (b) containing (inclusive) (a) containing 100 parts by mass of (a) a cyclic olefin monomer and 〇7 to 4 parts by mass. , a crosslinking agent having two or more polymerizable unsaturated bonds, and 1.15 to 15 parts by mass of (c) an organic peroxide-based thermal polymerization initiator having a half-life temperature of 1 3 5 to 200 ° C and (1) d) a polymerizable composition of a ring-opening metathesis polymerization catalyst is coated on a support, **•3 J3- a step of heating, ring-opening metathesis polymerization and crosslinking on the support 0 201238992 [Effect of the invention] The thermosetting card sound "丨* of the present invention has mechanical strength and water repellency with a sealing material, a semi-::= hydrocarbon resin, and the like; and the length: tensile fracture strength __ discoloration resistance The film of the present invention is fully described in the following description of the object of the present invention. [Embodiment] [Embodiment of the invention] The thermosetting crosslinked cyclic dilute resin of the present invention is composed of the present invention. The dilute hydrocarbon monomer of the raw material of the second product has a carbon atom The formed cyclic olefinic system and the coating 11 have a compound having a stone anti-carbon double bond. Specific examples thereof are a sulphate: & a monoterpene cyclic olefin, etc. Preferred (4) a cyclic olefin single system', Monomer: a monomer system having a reduced boxene system and a monomer having a reduced olefin ring. Specific examples of the η olefin monomer are a dinosaene, a dicyclopentadiene, a tetra = dicholine, etc. A polar group which may contain a hydrocarbon group such as a carboxyl group, an alkenyl group, a pyridyl group or an aromatic group, or an acid anhydride group, etc., is used as a substituent. Moreover, the rare monosystem includes a double bond of a norbornene ring. Further, it is also possible to have more bonds. From the viewpoint of improving the mold release property of the release film, it is preferred that the S-ene system is non-polar, that is, a lower alkyl group composed only of carbon atoms and hydrogen atoms. Monomers. Specific examples of non-polar lower-case olefinic monomers are dicyclopentadiene, A = pentylene, dihydrodicyclopentadiene (also known as tricyclic [5·2.1·02, 6] non-polar dicyclopentadienes such as 癸8-ene); -8- 201238992 tetracyclic [6.2.1.13,6_02,7]dodec-4-ene, 9-fluorenyltetracyclic [6.2. 1.13,6.02,7]dodec-4-ene, 9-ethyltetracyclo[6.2.1.13,6.02,7] 4-ene, 9-cyclohexyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-cyclopentyltetracyclo[6.2. 1.13,6. 〇2,7]12- 4 - alkene, 9 fluorene-methylenetetracyclo[6.2.1.1.13,6.22,7] 1,4--4-ene, 9-ethylenetetracyclo[6.2.1.1.13,6.22,7] Di-4-, 9-vinyltetracyclo[6 .2. .1.13,6. 〇2,7] dode-4--4-ene, 9-propenyltetracyclo[6 .2. .1.13,6. 〇2,7] dodeca-4-ene, 9-cyclohexenyltetracyclo[6.2.1.1.13,6. 02,7] dec-~-4-ene, 9-cyclopentenyltetracycline [6 .2, .1.13,6. 〇2,7]12-4-divalent, 9-phenyltetracyclo[6·: 2.1. 13,6.02,7] non-polar four of 1,4-ene Cyclododecene; 2-norbornene, i-mercapto-2-northene, 5-ethyl-2-lowene, 5-butyl-2-northene, 5-hexyl-2- Decalene, 5-mercapto-2-lowerene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norrene: alkene, 5-ethylidene-2-norrene , 5-vinyl-2-norboxene, 5-propenyl-2-norkenene, 5-cyclohexenyl-2-northene, 5-cyclopentenyl-2-norbornene, 5- Phenyl-2-northene Four 瓖 [9.2.1.02, 10.03, 8] fourteen-3,5,7,12-tetraene (also known as 1,4-methylene-1,4,4 mad, 9 8-tetrahydro-911 - s), tetracyclo [10.2.1.02, 11.04, 9] fifteen-4,6,8,13-tetraene (also known as 1,4-indolyl-l,4,4a,9,9a, Non-polar decenes such as 10-hexahydroindole; pentacyclic [6.5.1.1 3, 6.02, 7.09, 13] fifteen-4,10-diene, pentacyclic [9.2.1.14, 7.02, 10.03, 8] Fifteen-5,12-diene, hexagonal [6.6.1.13, 6.110, 13.02, 7.09, 14] hepta-4-ene or the like, a pentacyclic or higher non-polar cyclic olefin or the like. -9 - 201238992 From the point of view of the non-polar lower-case olefinic single system non-polar: which is easy to obtain and has good susceptibility to the film, the tetracycline is more selective, and the non-polarity is better: Pentacene and non-polar dicyclopentadienes. Phenene oxime system non-polar 葙 葙 [ [6.2.^6.02,7]12_9-浠+ Specific examples are four rings [6.2丄! 3,6.〇2,7]12_9_lean ester, tetracyclic, /j butyl-y cloth-4_sterol, forty-two-9-thin|capric acid, tetracyclic [6 2 Li36 diacidic acid, tetracycline [6·2" 13,6 〇2,7] twelve _9·field one·9-lean _4,5_ 5_lowering woman-2-acid acid vinegar, 2• Methyl _5 • drop, acid-lowering needle, acid 5 - sputum suspicion 9 Αe ─ 2 - retinoic acid methyl ester, vinegar 5 _ drop ... alcohol, 5 - drop ... alcohol, and so on, 2, acetyl I is thinner and more oxidized than the state: the ring-ring side is a specific example of cyclobutene, cyclopentene, and % octene 'cyclododecene. 5 division ...^ ^ 肀 肀 olefins and such substituents with substituents. These (a) cyclic dilute hydrocarbon single systems may be used alone or in combination of two or more. use. The amount of the mononuclear cyclic olefin to be added is preferably 40% by mass or less, and more preferably 2% by mass or less based on the total amount of the (4) cyclic thin tobacco monomer. When the amount of the monocyclic cyclic olefin to be added is 40% by mass or less, the heat resistance of the obtained heat-reducing parent-linked oxime hydrocarbon resin composition and the thermosetting crosslinked cyclic olefin resin film becomes sufficient. (a) a cyclic olefin monomer, (b) [a crosslinking agent having two or more polymerizable unsaturated bonds in addition to the (a)), and (c) a half-life temperature of 1 3 5 to 200 °. The organic peroxide-based thermal polymerization initiator of C and (d) the ring-opening-10-201238992 metathesis polymerization catalyst polymerizable composition' is heated to open core metathesis polymerization and cross-linking. (d) A ring-opening metathesis polymerization catalyst is a ring-opening metathesis polymerization of (a) a cyclic olefinic monomer. The polymerization catalyst is not limited to a specific catalyst. A complex compound in which an ion, an atom, a polyatomic ion, and/or a compound are bonded in plural by a transition metal atom can be used as the (d) ring-opening metathesis polymerization catalyst. The atomic systems of Groups 5, 6 and 8 (long-period periodic table, the same below) are used as transition metal atoms. The atomic system of each group is not particularly limited, but a preferred group 5 atomic system button, a preferred group of atomic molybdenum, a crane, and a preferred group 8 atomic system are hungry. The compound (d) ring-opening metathesis polymerization catalyst system ruthenium carbon-carbonate complex carbon-carbon-dif compound is excellent in catalytic activity at the time of bulk polymerization, and can obtain a small amount of residual unreacted monomer. Cross-linked ring-shaped returning smoke ^ Preferred (d) ring-opening metathesis polymerization catalyst series 8 group of cockroaches, moths

Complex compound. Specific examples of the nail carbon-derived compound are represented by formula (1) or formula (2)

(2) (1) 201238992 In the formulae (1) and (7), R^R2 is a ring-shaped or chain-like carbon number which is independently a halogen atom or may contain a dentate atom, an oxygen atom, a nitrogen atom, a ~, a phosphorus atom or a ruthenium atom. The second and sub-X2 lines are independent of each other and represent any anionic ligand. earth. ^ x L2 are each independently 'representing a neutral electron-donating compound. 'And : 2 series can be bonded to each other' containing a hetero atom, or an aliphatic two: an aromatic ring. Further, 'Ri, R'Xl, x2, LiL, and C are combined to form a plurality of chelating ligands. The hetero atom phase table (10) and the specific examples of the hetero atom in the present invention are nitrogen atoms (# s sulfur atom (8), germanium atom (As) ... Γ (), broken atom (p), # atom (Se From the viewpoint of the carbon-bonding compound, the preferred hetero atom system N, ruthenium, a particularly good hetero atom system N, and the neutral electron-donating compound are a macroene compound and a potted medium. The electron knives are active compounds of carbon having 3 hetero atoms. From the viewpoint of polymerization catalyst: a preferred neutral electron-donating compound contains two sides of a ruthenium: a dilute compound: preferably a miscellaneous The olefinic compound bonded to the carbon-carbon carbon plaque complex 3 hetero atom is more preferably a hetero atom-containing carbon ruthenium group containing a hetero atom of a carbene carbonogen C! A specific example of a hetero atom having a bulky substituted ut containing a hetero atom, which is a compound represented by the following formula (4), -12-201238992

σ

(3) (4) In the formulae (3) and (4), R3 to R6 each independently represent a hydrogen atom, a halogen atom or a ring which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a scale atom or a ruthenium atom. A hydrocarbon group having 1 to 20 carbon atoms in the form of a chain or a chain. R3 to R6 may be arbitrarily combined and bonded to each other to form a ring. Specific examples of the compound represented by the above formula (3) or formula (4) are 1,3-dicotyl imidazolidin-2-ylidene, 1,3-bis(1-adamantyl)imidazolidin-2 - Subunit, 1-3⁄4 hexyl-3-indenyl. Sitting sigma-2-ylidene, 1,3-diyl octa Benzimidazole-2-ylidene, 1,3-diisopropyl-4-imidazolin-2-ylidene, 1,3- Bis(1-phenylethyl)-4-imidazolin-2-ylidene, 1,3-dilyl-2,3-dihydrobenzimidazole-2-ylidene and the like. In addition to the compound represented by the above formula (3) or formula (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-111-1,2,4-triazole can also be used. -5-subunit, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, oxime, oxime, Ν', Ν'-tetraisopropylmethylene guanidine, 1,3,4-triphenyl- 4,5-Dihydro-1Η-1,2,4-triazole-5-ylidene, 3-(2,6-diisopropylphenyl)-2,3-dihydrothiazole-2-ylidene A hetero atom-containing carbene compound. -13- 201238992 An intermediate other than a carbene compound containing a hetero atom, which has been supplied from a t-heart metal: a sub-combination zygote. The neutral thunder + supply 有 eight neutral charge coordination type II, ethers, gambling, phosphine, sulfur shunt diamine: Sexual electrons: iL: thiocyanate. Preferably, the 'electron-producing compound is a phosphine-based electron-donating compound which is a tribasin-based scale. More preferably, the former is = an anion (anion) in the ruthenium (2); In the case of a negatively charged ligand, a specific example thereof is a halogen atom such as a fluorine atom (F), a gas atom (ci) i atom (βγ), an iodine atom (1), a diketonate group, or a substituted cyclopentadiene. a preferred alkoxy ligand, a aryloxy group, a carboxyl group, etc. a preferred anionic ligand, a cyclin atom, a more preferred ligand gas atom. In the above formula (1), X and L2 are bonded to each other to form a plurality of An example of the indene carbene complex of the integrated ligand is a Schiff base coordination complex represented by the following formula (5).

-14- .201238992 In the formula (5), "Z" represents an oxygen atom, a sulfur atom, a code atom, NR12, PR1 2 or AsR1 2 ' R12 is the same as those exemplified for R1 and r2. In the formula (5), R7 to R9 are each independently a hydrogen atom, a halogen atom or a monovalent organic group which may contain a hetero atom. Specific examples of the monovalent organic group which may contain a hetero atom are an alkyl group having 1 to 2 carbon atoms, a dilute group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 slave numbers, an aryl group, and a carbon number of 1 to 20 An alkoxy group, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group having a carbon number of ido, and a carbon number of 1. a 2 〇 alkoxy group, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkyl sulfonium group having a carbon number uo, an alkylsulfonic acid group having 1 to 20 carbon atoms, an arylsulfonic acid group, A phosphonic acid group, an arylphosphonic acid group, an alkylammonium group having a carbon number of 川~, an aryl ammonium group, and the like. These 1 which may contain a hetero atom may also be bonded to each other to form a ring. The alkyl group having a carbon number of 1 to 1 Å and the v 1 -valent organic group may have a substituent.

An alkyl group of 1 to 20 and a carbon number of 2 to 20 represent a hydrogen atom, a carbon number of an alkenyl group or a heteroaryl group, and these groups may be used.

A dish of 4-imidazolinyl) (3·201238992 Benji·1Η-section-1-ylidene) (r-p* 士丞)(—裱hexylphosphine)钌 dichloride, (ι,3- Dibasic, such as rice, sulphate, 2-ylidene) (3-methyl-2-butylene) subunit) (tricyclopentylphosphine) quinone dihydrate, phenylene leaf ^ soil base) (tricyclohexylphosphine) ) 钌二化化—::_八虱本和喃°2_2chloride, subunit [1,3-bis(1-phenylethyl]''sopromaline_2_subunit] Dicyclohexylphosphine) bismuth hydride, sub-succinct (1 丨 菜 -2,3 · dihydrobenzo-m-sodium 2-pyryl) (tricyclohexylphosphine Γ 'phenylene (tricyclic) Hexylphosphine) (triphenyl-2,3,4,5-tetra-111-1,2,4-triazole-5-ylidene) dichloride, (1,3-diisopropylhexahydropyrimidine) Derived 2-substrate) (ethoxymethylenetricyclohexylphosphine) ruthenium dimerate, subunit (1,3-difenyl -4-4-salt bite_2_subunit) Dichloride, (1,3-diyl-4-imidazolidinium-2-ylidene) (2-phenylethylidene κ-tricyclo-ylphosphine) ruthenium dihydrate, (1,3-didecyl) _4·Imidazoline_2_Subunit (10)· Benzoethylene)(tricyclohexylphosphine)phosphonium dichloride, (1,3二基基·4 5 ^臭_4♦坐琳·2·subunit)[(phenylthio)methylene](tricyclohexylphosphine) nail-Kt # ' (1n base_4'5_二漠_4_味D sitting on the _2_subunit) (2, pyridone ketone sulfhydryl) (tricyclohexylphosphine) ruthenium dihydride and other hetero atom-containing carbene compounds and " Preselectively combined ruthenium complex compound; phenylene bis(tricyclohexylphosphine) ruthenium dimerate, (3_methyl.2_butene subunit) bis(dicyclopentylphosphine) ruthenium a ruthenium complex compound in which two neutral electron donor compounds such as chloride are bonded; " = bis (1,3-dicyclohexyl such as rice mouth bit I subunit) 钌 two gasification, etc. The base of the double (1,3-diisopropyl one meter...subunit) Shu two gasification temple of the two kinds of heterogeneous carboniferous compound bonding in the complex compound-16 - 201238992 seat combination? Forming a plurality of 8-integrated

R 曱 式 ^ ' MeS represents the shelf base ° Han 7 and r8 are each a nitrogen atom or a plum. The methyl group. Rl3 and R are 4 independently, and represent hydrogen (8), or a monovalent organic group which may contain a hetero atom. Further, the amount of Γΐ, ', is the same as the above-mentioned R7 to R9 in the description of the formula (5). Specific examples of the complex compound represented by the formula -4^' (2) are (1,3-dioxax#oxazolidin-2-yylidene) (phenylvinylidene) (tricyclic) Hexylphosphine) indole-2-ylidene v bis(f dibutylvinylidene) (1,3-diisopropyl-4-imidazolinium imidazolinium hydrazine plant pentylphosphine) bismuth hydride, double d , 3·dicyclohexyl_4_subunit) phenylvinylidene quinone dihydrate. The compound of the formula (3) or (4) which is represented by the formula (3) and has a ligand. U 9 nail 5; carbon olefin complex system can be obtained by (4) 〇r one, dating page, (b) Tetrahedr〇n. Lett., 1999, 40th lane, 2247 pages, (c) international Public M. The method is used to produce the amount of the 201238992 (d) ring-opening metathesis polymerization catalyst described in A. 2003/062253, etc., ((d) ring opening complex a metal atom in the polymerization catalyst: (a) ring The molar ratio of the olefin monomer is usually 1:2,000 to 1:2,00 Å, 〇〇〇, preferably 1:5, 〇〇〇~1:1, ()()()〇(^ It is more preferably in the range of 1:10,000 to 1:500,000. By making the amount of the (开) ring-opening metathesis polymerization catalyst to (a) the molar ratio of the cyclic olefin monomer to 1/2,000,000 or more, A sufficient polymerization rate can prevent the monomer remaining in the polymer, or the crosslinking degree of the crosslinked polymer is lowered, or the obtained thermosetting crosslinked cyclic olefin resin composition and the thermosetting crosslinked cyclic thin hydrocarbon resin film The heat resistance is lowered. By making the amount of (d) ring-opening metathesis polymerization catalyst to 1/2 of the (a) cyclic olefin monomer, the production cost can be reduced, and by The reaction rate is suppressed to be too fast, and the thermosetting crosslinked cyclic olefin resin film in the bulk polymerization described later is used.

Easy to shape. N is used to control the polymerization activity and increase the polymerization rate. (d) The ring-opening metathesis polymerization catalyst may be used in combination with an active agent (auxiliary catalyst). Specific examples of the active agent are alkyl, amide, alkoxylate and aryloxy compounds of aluminum, vanadium, tin and antimony. More specific examples of the active agent are trialkoxy aluminum, triphenyloxy aluminum, dialkoxy aluminum alkyl, alkoxydialkyl aluminum, trialkyl aluminum, vaporized dialkoxy aluminum, gasification Alkoxyalkylaluminum, a dialkyl chloride-specific compound; a ruthenium compound such as trisodium oxyhydroxide; a titanium compound such as tetra-oxygenated titanium; or a tin such as tetraalkyltin or tetraalkoxide a compound; a compound of tetra-oxygenoxy group; dimethyl mono IU Xi, dimethyl dioxane, diphenyl dichlorodecane, tetrachloro decane, bicycloheptenyl fluorenyl monooxane, stupid base a decane compound such as chlorodichlorosilane, dihexyldioxane, phenylmonochloride, methyltrichloromethane or the like. 201238992 The amount of active agent used, Gd) pg is an atom: the stem of the activity ^: the gold in the catalyst! The molar ratio of the greening agent is usually 1: 〇 〇 5 is 1 and more preferably 1: 0.5 to 1:1 。. . 圭 环 复. Decomposition ^ I ° 卽 卽 polymerization rate for the purpose, (4) open and the system can be used together with polymerization regulators. The eight types of polymerization regulators are diphenylphosphine, triphenylphosphino), gamma, 14^bis(diylphosphino)penta-(tetra), phenylphosphino), butadiene, bis(diphenyl, etc.) Use the 路, 酉, guess, etc. Louis test. Use $, relative to 1 mole of \ & media, usually 〇〇1 50 stem and ? metathesis polymerization touch. 1~50 m, preferably 0.05~1〇莫耳. Hardened Π:::: Γ 性 交 ( 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ In any of the steps of the fish, it is preferable to use a block polymerization method in view of the fact that the fish does not require a solvent to remove the composition: The method has the following steps: (8) [except for the (4) half-life temperature 4 135 crosslinking agent], (c) 1 minute starting agent, and (4) open-loop metathesis poly 2: with: oxidation In the presence of a thermal polymerization initiator, heating, ring-opening metathesis polymerization, and eliminator:,::: a system containing a heat-containing olefin resin film, 2 -, a) % olefin monomer, (b) [crosslinker of (4) or more polymerizable unsaturated bond], (c) 1 minute 201238992 half-life temperature 135~20 (TC organic peroxide a polymerizable thermal polymerization initiator and (d) a polymerizable composition of a ring-opening metathesis polymerization catalyst, which is formed into a film shape by heating, ring-opening metathesis polymerization, and crosslinking in the presence of an additive used as needed It is considered that (a) the cyclic olefin single system is subjected to ring-opening metathesis polymerization to obtain a cyclic olefin polymer, and more preferably, the cyclic olefin polymer is subjected to ring-opening metathesis polymerization or ring-opening metathesis polymerization. At the same time, crosslinked to obtain a crosslinked cyclic olefin polymer. The three-dimensional crosslinked structure of the cyclic olefin polymer, the thermosetting crosslinked cyclic olefin resin composition and the thermosetting crosslinked cyclic olefin resin film is It was confirmed for the solubility in 1,2-dichlorobenzene. The cyclic dilute polymer was immersed in 1,2-dichlorobenzene at 23 C for 24 hours, and the metal mesh of 8 〇 mesh was used for consideration. The mass of the insoluble portion of the polymer in solution, divided by the original The degree of crosslinking determined by the mass of the former polymer is preferably 70% by mass or more, more preferably 8% by mass or more, and particularly preferably 5% by mass or more. By 70% by mass or more, More favorable heat and mechanical strength can be obtained, and contamination of the substrate, the mold, the pressurizing device, and the like by the uncrosslinked component can be suppressed. The polymerizable composition of the raw material of the thermosetting crosslinked cyclic olefin resin composition of the present invention The material contains (b) a crosslinking agent having two or more polymerizable unsaturated bonds. Specific examples of the crosslinking agent are pentaerythritol bis(indenyl) acrylate and 1,6-hexanediol di(methyl). Acrylate, 1> 2_ethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol II (Mercapto) acrylate 'neopentyl glycol di(meth) acrylate, tricyclodecane dimethanol di(methyl) propylene-20 - 201238992

Ss_S曰, diozomethylpropane tri(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate dipentaerythritol (Meth) acrylate having two or more polymerizable unsaturated bonds, such as acrylate. One type or two or more types of crosslinking agents having a polymerizable unsaturated bond can be used. With respect to 100 parts by mass of the (a) cyclic olefin monomer, [in addition to the (a), the crosslinking agent having two or more polymerizable unsaturated bonds] is preferably 0.7 to 40 parts by mass, preferably It is 〜3〇 parts by mass, more preferably 2~2〇 parts by mass, and particularly preferably 4 to 10 parts by mass. (8) When the content of the crosslinking agent having two or more polymerizable unsaturated bonds other than the above (4) is too small, the mold release property, water repellency, and temperature resistance of the thermosetting crosslinked cyclic olefin resin film before and after heating are high. The discoloration is reduced. On the other hand, if the content of the crosslinking agent having two or more polymerizable unsaturated bonds is excessive in addition to the above (a), the polymerizable composition cannot be formed into a film. The polymerizable composition of the raw material of the thermosetting crosslinked cyclic olefin resin composition of the present invention contains (c) an organic peroxide-based thermal polymerization initiator having a one-minute half-life temperature of 135 to 2 〇〇 C. Specific examples of the thermal polymerization initiator are 1,6-bis(t-butylperoxyoxy)hexane, 13-bis-tributylperoxyisopropyl)benzene and the like. One type or two or more types of organic peroxide-based thermal polymerization initiators having a half-life temperature of from 135 to 200 ° C can be used. ^ (c) The one-minute half-life temperature is 135 to 200 with respect to 1 part by mass of the (a) cyclic olefin monomer. The content of the organic peroxide-based thermal polymerization initiator is 545 parts by mass, preferably i 5 to 1 part by mass, more preferably 2 to 8 parts by mass of 201238992. (c) 1 minute half-life temperature is When the content of the organic peroxide-based thermal polymerization initiator of 135 to 2〇〇t>c is too small, the mold release property, mechanical strength, water repellency, and high temperature resistance of the thermosetting crosslinked cyclic olefin resin film before and after heating are increased. The discoloration property is lowered, and there is also a possibility that the polymerizable composition cannot be polymerized. On the other hand, (c) if the content of the organic peroxide-based thermal polymerization initiator having a one-minute half-life temperature of 135 to 200 ° C is excessive ' There is a possibility that the polymerizable composition cannot be polymerized. Further, the organic peroxide-based thermal polymerization initiator (the minute temperature is lower than 135°) may not polymerize the polymerizable composition: 虞. For the purpose of improving the properties of the film for various purposes and purposes, and the improvement of the moldability, the polymerizable composition of the raw material of the bicyclic olefin resin composition of the present invention may have various additives. Specific examples of additives Materials, defoamers, foaming agents, greening agents, flame retardants, wetting agents, dispersants, mold release agents, etc. In order to improve the cross-linking of cyclic hydrocarbons, take D The durability of the material and the left-twisting property are preferably antioxidants and light stabilizers. ', specific examples of female antioxidants are benzene, toluene; hydroquinone, p-tert-butylcatechol , 2,5_二醌, the hydrazine hydroquinone; di-tert-butyl-p-cresol: hydroquinone: I-based hydroquinone and other ages; ring-sintered copper or octenoate Copper bee soil bond, pyroyl guanidinium ammonium, trimethyl benzyl maleate, * dimethylated dimethyl sulfonium salt; kedi or methyl ethyl ketone Acid salt or dibutylamine chlorhexidine hydrochloride; triethylamine I amine hydrochloride. These anti--22- 201238992 oxidant species and mechanical properties at maturity, f system can be cross-linked cyclic olefin polymer The high temperature is suitable for selection. The compatibility of the conditions for the formation of workability, preservation stability, etc. is high, = good (four), because it is qualitative with the cross-linked cyclic smelting polymer. Antioxidant #丨焱溽The durability and the storage stability can be used in one type or in combination. The amount of the anti-tanking agent is usually 0.001 to 10 parts by mass based on the amount of the (a) cyclic dilute hydrocarbon monomer. Specific examples of the stabilizer include a hindered amine light stabilizer (HALS) compound. Specific examples of the guanidine-resistant amine stabilizer are 4-thio-2,2,6,6-tetramethylpiperidine and cumene. Base_4_hydroxy-2,2,6,6-tetradecylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetradecylpiperidine, i_(4_third 2-butenyl)-4-hydroxy-2,2,6,6-tetradecylpiperidine, 4-stearyloxy-2,2,6,6-tetradecylpiperidine, 1 _Ethyl-4-salicylideneoxy-2,2,6,6-tetramethyl stilbene, 4-methylpropenyloxy_ 1,2,2,6,6-pentamethylpiper Pyridine, 1,2,2,6,6-pentamethylpiperidine _4•yl-β(3,5-di-t-butyl-4-yl-hydroxyphenyl)-propionate, 1-benzyl -2,2,6,6-tetramethyl-4-piperidinyl maleate (maleinate), (di-2,2,6,6-tetradecylpiperidin-4-yl)-hexane Acid ester, (di-2,2,6,6-tetradecylpiperidin-4-yl)-sebacate, (ditetradecyl-2,6-diethyl-?). D--4-yl)-sebacic acid g, (di-I-Allyl-2,2,6,6-tetramethyl-piperidin-4-yl)-phthalate, Mercapto-2,2,6,6-tetramethyl 0 bottom bit-4-yl-acetamidine, trimenic acid-tris-(2,2,6,6-tetramethyl-bite-4 - Ester, 1-propenyl 4- 4-benzyloxy-2,2,6,6-tetramethylpiperidine, dibutyl-malonic acid-:-(12,2,6,6- Pentadecyl-piperidin-4-yl)-ester, dibenzyl-malonic acid-:-(12,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) _ ester, dimercapto-bis-(2,2,6,6-tetramethyl-23- 201238992 piperidin-4-yloxy)-nonane, tri-(1_yl)-sub-allate, three servants Propyl·2,2f6 6_,2'6'6·Tetramethyl- _4-ester, N,N,-bis-(2,2,6,6 ' 7 base brigade ·4-base two Ethylamine, ethyl ketone _4 cases of two fixed '4 hexamethylene], 6-bite, 4 · arylamino-2 2 6 / ethane with amine (4), 6,6-tetramethyl? ^ ^ ^ , 2,6,6·tetramethylpiperidine, N,N,-bis-(2,2,6,6-tetramethylpiperidine-4_yl_ ◎,-bis-(2, 2,6'6-tetramethyl 0 Chen bite ^1 butyl 'hexamethylenediamine, phantom κ, χτχ 疋 MM,-dicyclohexyl-(2· ΪΓΛ ΓΓΓ^ I 7 methyl ethyl), Quiche from Wuyi Brigade; λ7[ν"Γ;7'1,2,2^ :Μ (,,6,6,曱基...-Kizhou cross-linking =::= The type and amount of stabilizer compound can be equal to : The parts are: the conditions of the mechanical properties of the temperature and the stability of the storage 4 are suitable for selection. 枋 π number and the etch field "丄 丄 刻 can be 1 type or combined with 100 parts by mass (4) ring Dilute hydrocarbon monomer, the hindrance of the female first female formula compound is usually 〇._~(4) parts. The specific material of the filler is 丨彳石々I Λ ^ ^ 彳 矽 矽 、 、 、 、 、 Inorganic fillers such as calcium carbonate, gas oxidized magnesium oxide, clay, etc.; organic fillers such as wood powder, poly-beads, polystyrene beads, etc. Filling materials improve the shrinkage of cross-linked bismuth bismuth bismuth Physical properties such as elastic modulus, thermal conductivity, and electrical conductivity. The particle size of the filler, such as the shape, the aspect ratio, and the grade, are appropriately determined according to the physical properties of the U-shaped olefin polymer. 〇〇-24- 201238992 A mass of the (a) cyclic olefin monomer, and the filler is preferably used in an amount of 5 to 400 parts by mass, more preferably 10 to 300 parts by mass. Specific examples of the release agent are polyoxygenated oil, zinc stearate, etc. The release agent is a function of improving the formability, mold release property, and handleability of the film, and imparting a lubricant property to the film. 1 〇〇 mass of (a) cyclic dilute hydrocarbon monomer, the amount of the release slip agent is preferably 〇. ^ 200 parts by mass. (a) a cyclic olefin monomer, (b) [a crosslinking agent having two or more polymerizable unsaturated bonds in addition to the (a)), and (c) a one-minute half-life temperature of 135 to 200 ° C The organic peroxide-based thermal polymerization initiator and (d) the polymerizable composition of the ring-opening metathesis polymerization catalyst are heated, ring-opened metathesis polymerization, and crosslinked in the presence of an additive used as needed. (d) The open % metathesis polymerization catalyst may be dissolved or suspended in a small amount of an inert solvent as needed. Specific examples of the solvent are chain aliphatic hydrocarbons such as n-pentane 'n-hexane, heptane, flowing stone butterfly, mineral oil, etc.; cyclopentene, % hexane, methylcyclohexane, dimethylcyclohexane An alicyclic hydrocarbon such as an alkane, a trimethylcyclohexane, a decyl hexane, a diethylcyclohexane, a decahydronaphthalene, a dicycloheptane, a tricyclo: alkane, a hydroquinone or a cyclooctane; An aromatic hydrocarbon such as benzene, toluene or dioxane; a nitrogen-containing hydrocarbon such as 2 n-nitromethane, nitrobenzene or acetonitrile having an alicyclic ring and an aromatic ring such as anthracene or tetrahydronaphthalene; diethyl ether, tetra "; etc. 3 oxygen smoke special. Preferred solvents are aromatic hydrocarbons, aliphatic & long hydrocarbons, and hydrocarbons having an alicyclic and aromatic ring. A liquid aging preventive agent or a plasticizer which is reduced in the activity of the polymerization catalyst can be used as a solvent. , (a) olefin monomer, (b) [crosslinker having 2 113⁄4 yJs on the poly -8 δ unsaturated bond in addition to the (a)], (c) 1 minute half-life temperature - 25- 201238992 The viscosity of a polymerizable composition of an organic peroxide-based thermal polymerization initiator of 1 3 5 to 2 0 0 C, (d) a ring-opening metathesis polymerization catalyst, and an additive as needed, at room temperature The 'system is also dependent on the thickness of the desired film, but is usually from 3 to 30,000 Pa·s', preferably from 5 to 500 Pa·s. The viscosity of the above composition is (a) a cyclic olefin monomer, (b) a crosslinking agent having two or more polymerizable unsaturated bonds in addition to the (a), and (c) a one minute half-life temperature. It is adjusted by the type and amount of the organic peroxide-based thermal polymerization initiator of 135 to 200 ° C and (d) the ring-opening metathesis polymerization catalyst. The thermosetting crosslinked cyclic olefin resin composition of the present invention can be produced by heating the above polymerizable composition to carry out bulk polymerization and crosslinking. A specific example of the method for producing the thermosetting crosslinked cyclic olefin resin film of the present invention is a method in which the above polymerizable composition is washed or applied onto a baffle body, and heating, bulk polymerization, and crosslinking are carried out. A method in which a polymerizable composition is heated in a mold, a bulk polymerization, and a crosslinking. The method of casting or coating the above polymerizable composition on a support is carried out by heating, bulk polymerization, and crosslinking, and it is more preferable because a thin and uniform film can be continuously produced. A generally known material such as resin, glass, or metal can be selected as the above support. Specific examples of the resin are polyesters such as polyethylene terephthalate, polyethylene terephthalate, polycarbonate, polyarylate, polypropylene, polypropylene, polyene, nylon, etc. A styrene; a fluororesin such as polytetraethylene or the like; preferably a polyester which is easy to obtain. If the material is metal or resin, the preferred shape of the support is a cylinder or a belt. A preferred support system is to find an easy and inexpensive resin film. The method of applying the above polymerizable composition to the support is not particularly limited. Specific examples of the method are a spray coating method, a dip coating method, a coating method, a curtain coating method, a die coating method, a slit coating method, and the like. -26-201238992 The above polymerizable composition is heated as needed until the temperature at which (d) the ring-opening complex catalyst exhibits activity is carried out to carry out bulk aggregation. The temperature at the time of polymerization and crosslinking is usually from 0 to 250 ° C, preferably from υ to 2 ° ° C. The heating method of the above polymerizable composition is not particularly limited. The specific example of the heating method is a method of heating on a hot plate, and the method of heating (heat M) while pressurizing the press using m 1 is performed. A method of using a heating furnace by a method of pushing a heated roller. The reaction time at the time of polymerization Λ ^ can be appropriately determined depending on the amount of the polymerization catalyst, the amount of the organic peroxide-based thermal polymerization initiator added, the heating temperature, and the like, and is usually from 1 minute to 24 hours. The polymerizable composition is heated to have (b) an organic peroxide-based thermal polymerization initiator having a half-life of 135 to 200 ° C, and (b) (in addition to the (a), two The crosslinking agent of the above polymerizable unsaturated bond] is crosslinked. The crosslinking reaction is carried out after ring-opening metathesis polymerization or simultaneously with ring-opening metathesis polymerization. The crosslinking reaction temperature must be attained with the temperature at which the ring-opening metathesis polymerization catalyst exhibits activity, and (4) the amount of the ring-opening metathesis polymerization catalyst added, the organic peroxide-based thermal polymerization initiator exhibiting activity, and the organic peroxide. The amount of the thermal polymerization initiator added is related. Further, it is usually 130 to 250 ° C, preferably 15 to 230 ° C. The heating time is not particularly limited, and is usually from several minutes to several hours. = The heating method of the above polymerizable composition is not particularly limited. Specific examples of the heating method include a method of heating on a hot plate, a pressurization using a punching machine, and a method of heating (hot pressing) by means of a roll having been applied with ',, and '. A method using a heating furnace or the like. -27-201238992 As a method of crosslinking the above-mentioned polymerizable composition, a method of heating by adding an organic peroxide-based thermal polymerization initiator is mentioned, and (A) adding a conventional diazonium compound a method of heating a radical generating agent such as a non-polar radical generating agent; (B) a composition of a conventional photopolymerization initiator, which is irradiated with light or an electron beam to cause polymerization and crosslinking reaction. The method or the like may be used in combination with a method in which an organic peroxide-based thermal polymerization initiator is added and heated. The cyclic olefin polymer is also crosslinked by a crosslinkable cyclic olefin monomer to be carried out after polymerization or simultaneously with polymerization. It is more preferable to carry out the crosslinking at the same time as the polymerization because the thermosetting crosslinked cyclic olefin resin film of the present invention can be industrially advantageously obtained in a smaller number of steps. In addition, the term "simultaneously" as used herein refers to a ring-opening metathesis polymerization reaction and a crosslinking reaction by one-step heating, a temperature at which a catalyst is activated according to a ring-opening metathesis polymerization, and (c) a half-life temperature of 丨 minute. The temperature at which the organic peroxide-based thermal polymerization initiator is activated at 1 3 5 to 200 ° C can be considered in the case where (i) the ring-opening metathesis polymerization occurs first, and then the parent reaction continues to occur. In the case of (ii) the cross-linking reaction occurs first, and then the ring-opening metathesis polymerization reaction continues, and the ring-opening metathesis polymerization reaction and the cross-linking reaction occur at the same time. The concept of "land". The (a) cyclic olefin single system having two or more carbon-carbon double bonds is used as the crosslinkable monomer used in the method of (A). Specific examples of the cyclic olefin monomer are dicyclopentadiene and tricyclopentadiene. The crosslinking density can be controlled by the amount of the crosslinking monomer and the heating temperature at the time of polymerization. The amount of the crosslinkable monomer used is appropriately defined by the amount of the crosslink density according to the use of the film, in the various amounts of -28-201238992. The preferred amount of the crosslinkable monomer and the ratio of the crosslinkable monomer are various, so that it is not particularly limited to 1 to 100 mol% of the ring-shaped flue-cured monomer. The specific example light or electron ray of the method of the father-in-law is formed by the block (4) and cross-linking after the polymerization, preferably under the oxygen and water. Specific examples of the bulk polymerization and crosslinking method are: (1) an inert gas method such as nitrogen emulsion or helium gas, & τ bulk polymerization and crosslinking; and a block polymerization and a lipid film covering under vacuum The method of applying to the support (3) is a method of polymerizing and cross-linking the above-mentioned composition on a tooth in a tree shape in a closed block. The specificity of the resin film =: exemplified by the branch body. When the polymerization and crosslinking are carried out in the presence of oxygen or water, the surface of the film of l | 、 斤 and 侍 侍 is oxidized, and it is difficult to exert the desired release property. The thickness of the urethane-based olefin resin film of the present invention is as follows, and the appropriate values are various according to the use, so there is no particular limitation: usually 0.5 to 5,000 μm. From the viewpoint of the above, it is preferable that the degree of the first degree is 5 to "O'. The thermosetting crosslinked cyclic olefin oxime of the present invention, the surface of the film may be smooth, and the uneven shape may be processed through the ruling. A layer containing a heterogeneous material of an organic substance, an inorganic substance, a metal, or the like can be formed in the heat of the present invention by a conventional surface treatment technique such as gas phase reaction, coating, vacuum evaporation, ion plating, sputtering CVD, electroless plating, or the like. A hardenable crosslinked cyclic olefin resin composition and a surface of a thermosetting crosslinked ring -29-201238992 olefin resin film. For example, an anti-release property including Si〇2, MgF2, fluororesin or the like is provided on the surface layer of the film. The film of the material is surface-treated with a fluorine gas or a CF-based precursor, and the surface of the film may be fluorinated to the thermosetting crosslinked cyclic olefin resin film of the present invention, and the film may be improved without fluorination. Modularity. Finally In the thermosetting crosslinked cyclic olefin resin composition of the present invention, the above-mentioned (a) cyclic olefin single-system lower-case-ene monomer is preferred. (b) above (in addition to the above (4), The cross-linking agent of two or more polymerizable unsaturated bonds is a (meth)acrylic acid Sa having two or more polymerizable unsaturated bonds. Preferably, the above (d) ring-opening metathesis polymerization catalyst ruthenium carbene is misaligned. Olefin resin single system drop with two upper polymerizable cyclic metathesis-like olefin tree single system drop with two upper polymerizable cyclic metathesis compositions terpene-based polyunsaturated polymerized contact grease film decene system above In the method for producing a thermosetting crosslinked ring of the present invention, the above preferred (&) cyclic olefin monomer is preferably (b) above (in addition to the (a) The cross-linking agent of the unsaturated bond has two (meth) acrylates which are bonded, preferably the above (d) open-cell nail-like complex. Further, the thermosetting cross-linking of the present invention In the method for producing a ring, the above (&) cyclic olefin monomer is preferred. Preferably, the above (b) [in addition to the (a), the crosslinker of the unsaturated unsaturated bond] has two (meth) acrylates bonded by a bond, preferably the above (d) opener Carbon thin complex. ' 3 〇 - 201238992 [Examples] Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples, which are defined by the examples. Examples and Comparative Examples The parts and % are determined based on the mass unless otherwise specified. (1) The water contact angle of the thermosetting crosslinked cyclic olefin resin film is controlled by a fully automatic contact angle meter (Concord) Surface Science (Unit) DM-70 1), using ion-exchanged water as a solvent, dropping 〇6pL (〇6 μL) of droplets' by Θ/2 method to be processed into a 5〇ninix50mm resin film The contact angle of the water "The greater the water contact angle, the higher the water repellency. (2) Tensile properties of the thermosetting crosslinked cyclic olefin resin film The tensile elongation at break and the tensile breaking strength of the thermosetting crosslinked cyclic olefin resin film were measured in accordance with JIS K687 1. The greater the tensile elongation at break of the film, the higher the airtightness of the metal mold, and the formation of the burrs of the sealing resin can be suppressed. The higher the tensile breaking strength of the film, the more the film is less likely to be broken, and the leakage of the sealing resin can be suppressed. (3) The peeling force of the semi-cured sheet of the thermosetting crosslinked cyclic olefin resin film is punched out into two sides of a prepreg for printed circuit board laminates (FR_4 R1661 (G) GB type manufactured by Panasonic Electric Co., Ltd.) of 300 mm x 300 mm. The release film of the example or the comparative example was clamped and inserted into a vacuum punching machine at 1.0 MPa and 18 Torr. (: After heating and hardening for 7 minutes, it was cooled to 4 (TC, the sample obtained was taken out from the vacuum press machine. The test piece of 25 mm x 150 mm was cut out from this sample, and the peeling force of 18 degree was measured according to JIS κ 6854_2. Force is used as the initial peeling force on the prepreg. -3 1- 201238992 The sample taken out from the vacuum press is stored in an oven at 95 °C for 3 days, and the test of cutting out 25 mm X 150 mm from the sample For the sheet, the peeling force of 180° was measured according to j I s κ 6 8 5 4 - 2. The peeling force was taken as the peeling force to the prepreg after heating. The smaller the peeling force to the prepreg, the higher the mold release property. The thermochromic crosslinked cyclic olefin resin film is heated and discolored. The resin film which has been punched out into a 50 mm x 105 mm film is stored in a 95 〇 oven, and taken out after 3 days, using a Konica-Minolta Sensing (color) color difference meter CR- The color difference of the film taken out was measured by 400. The smaller the value, the higher the high-temperature discoloration resistance. Examples 1 to 1 3 and Comparative Examples 1 to 1 5 Two or more polymerizations of the masses shown in Tables 1 and 2 were obtained. The cross-linking agent and stabilizer of the unsaturated bond are dissolved in a bicyclic ring containing 92.6% by mass. The reaction stock solution was obtained from a mixture of pentadiene and 7.4% by mass of 5-ethyl-2-pyrene in a reduced monomer mixture. Next, the masses shown in Table 2 and Table 2 have the formula (7). The structure of the catalyst, organic peroxide-based thermal polymerization initiator was added to the above reaction stock solution, mixed with a flow mixer (Line Mixer), and applied to a polyacetate having a thickness of 0.075 mm at 25 ° C. On the carrier film made of ethylene glycolate, casting film was formed, and then the same carrier film prepared separately was laminated on the coating layer immediately. Then, 'opening at 200 ° C for 3 minutes to perform ring-opening metathesis Polymerization and crosslinking to obtain a resin film. The results are shown in Tables 1 and 2. -32- 201238992

(7) 201238992 Embodiment 13 〇〇ρ ρ τ-^ ρ ο τ—Η ο (Ν 1 1 〇Ι—Η CN 〇VO oo oog Ο On v〇CN Example 12 Ρ 〇ρ ρ ο Γ"Η ο Ο CN 1 1 1 〇1 ι> 〇\ S r- <N (Ν in soo CN Example 11 ο ο ρ ρ ο 1-Η Ο Ο (Ν 1 1 1 ο 1 1 卜ρ r—Η »-Η inch Pooo Os OO CN Embodiment 10 ο ο r Η Ο ο ο ο Η 1 1 1 ο <Ν 1 ί 〇1 1 1 g w-^ On Let soo <N Example 9 100.0 Ο ρ ρ ρ Ι- ο ο ο 1 1 1 1 1 〇»ri 1 1 1 to s ON soo rJ 00 o Example 8 100.0 ο ^Η ο ο ρ Ο ui 1 1 1 1 1 〇tn 1 1 1 CS s inch mood oo 〇\ d Example 7 100.0 ρ ρ * - Η ο r * H ο 1 1 1 1 1 ο νί 1 1 1 oo o tH o 卜 o 1 - ^ CN d Example 6 ο ο ρ ρ ρ ο Ο CN 1 1 1 1 1 ο 1 1 1 卜σ\ s CN o c> o «-Η 卜 o Example 5 ο ο ρ ρ ρ ρ Ο CN 1 1 1 1 1 ο ο 1 1 1 oo s inch dsosd <N 00 o Embodiment 4 ο ο ρ »-Η ρ ρ ο Ο CN 1 1 1 1 1 ο 1 1 1 卜»~Η s ro 卜αί goso fS 〇\d Real Example 3 100.0 ρ 1"Η ο r·^ ο ι—Η ο 1-Η Ο (Ν 1 1 1 1 1 ρ 1 1 1 Bu «-Η 100.9 inch (Ν QC Ό CN 〇odo CN Example 2 100.0 Ο ο ρ ο Η Ο (Ν 1 1 1 1 ο »ri 1 1 1 1 卜 101.2 m On inch sooo 〇\ 00 o Example 1 100.0 Ο ο «-Η ο ο Ο (Ν 1 1 1 ο ν*ί 1 1 1 1 1 oo sv〇cn »—H pood «η inch fN olefinic monomer mixture stabilizer Αυ stabilizer Β 2) stabilizer c3) stabilizer D4) thermal polymerization initiator α5) thermal polymerization Starting agent β6) Thermal polymerization initiator c7) Thermal polymerization initiator d8) Trimethylpropane trimethacrylate 9) Pentaerythritol triacrylate (9) Dipentaerythritol hexaacrylate η) Tricyclodecane dimethanol diacrylate Ester ι2) Polyethylene glycol #200 diacrylate 13) Polyethylene glycol #400 diacrylate M) 钌 Catalyst 15) Water contact angle (°) MD tensile elongation at break (%) MD tensile strength at break (MPa) Initial peeling force on prepreg (N/25mm) Peeling force on prepreg after heating (N/25mm) Discoloration after heating (ΔΕ氺) Cough (Di ah) - inch ε- 201238992 <Ν< Comparative Example 15 〇〇〇〇ρ ο 1 1 οο 1 1 1 〇in 1 1 1 1 1 1 1 1 1 Comparative Example 14 〇〇〇〇ρ ο 1 <Ν 1 1 1 1 〇iri 1 1 1 Bu 1 1 1 1 1 1 Comparative Example 13 100.0 ρ 〇ο ο 1 l 1 1 1 1 1 〇in o 〇\ m vo to — S Comparative Example 12 100.0 〇q ο ο 1 1 1 1 1 1 1 1 〇us 1 os; SO vd cn uS 躁g (Ν Comparative Example 11 100.0 〇ο ο ο 1 1 ! 1 1 1 1 〇wS 1 1 o (N ON m cs is o 卜 寸 · Comparative Example 10 100.0 〇ο ο ρ ο 1 1 1 1 1 ο u-ϊ 1 1 1 1 1 1 1 1 1 Comparative Example 9 〇〇〇ο ο ο ο 1 1 1 1 1 ο uS 1 1 1 o S inch 〇 Comparative Example 8 100.0 〇ο ο ο (Ν ο 1 1 1 1 1 ο uS 1 1 1 o σ\ Ό JO clock P 15.10 Comparative Example 7 〇〇〇ρ ο ο 1 I 1 1 1 1 ο iri 1 1 1 o uS On 卜·!〇m Comparative Example 6 100.0 〇ο ρ ρ 1 1 1 1 1 〇uS 1 1 1 1 σ\ CN 卜r*^ (N - ο ο Comparative Example 5 100.0 q ο ο ρ 1 1 1 1 ο 1 1 1 1 1 (N 00 O od -L〇CN (寸 inch ' Comparative Example 4 100.0 〇ο ο ο ο (Ν' 1 1 1 1 1 ο 矣1 1 1 r^; 1 1 1 1 1 1 Comparative Example 3 100.0 〇ο ρ ο ο (Ν 1 1 1 1 1ο 1 1 1 i Pair (N 戋〇〇CN s Os Comparative Example 2 〇〇〇ρ ρ ο ο CN 1 1 1 1 1 1 1 1 1 r- ΓΛVΓΛvd 〇棋 o ci Comparative Example 1 100.0 〇 ρ ρ ρ 1 1 1 1 1 ' 1 1 1 1 1 卜m C-; in inch CN garlic ON decene-based monomer mixture stabilizer Αυ stabilizer Β 2) stabilizer C3) stabilizer D4) thermal polymerization Starting agent α5) thermal polymerization initiator β6) thermal polymerization initiator c7) thermal polymerization initiator d8) trimethylpropane trimethacrylate 9): pentaerythritol triacrylate (9) dipentaerythritol hexaacrylate H) three Cyclodecane dimethanol diacrylate|2) Polyethylene glycol #200 diacrylate 13) Polyethylene glycol #400 diacrylate|4) Cerium catalyst 15) Water contact angle (°) MD tensile elongation at break Degree (%) MD tensile strength at break (MPa) Initial peeling force on prepreg (N/25mm) Peeling force on prepreg after heating (N/25mm) Discoloration after heating (ΔΕ*) 刼哒(铋峒甶) -ιηε- 201238992 1) BASF 曰本(股)制IRGANOX565 2) BASF 曰本(股)制IRGANOX1010 3) 股KAADEKASTAB HP-10 4) BASF 曰本(股)制TINUVIN770

5) Kayalene 6-70, a chemical AKZO (stock) 1 minute half-life temperature 150 〇C

6) Peroyl TCP 1 minute half-life temperature 92.KC

7) Nyper E 1 min half-life temperature 130 ° C

8) Chemical AKZO (share) system Perkadoxl4R-Gl minute half-life temperature 185 ° C

9) Light Ester TMP by Gongrongshe Chemical Co., Ltd.

1〇)Chengrongshe Chemical Co., Ltd. Light Acrylate PE-3A

11) Gongrongshe Chemical Co., Ltd. Light Acrylate DPE-6A

12) NK Ester A-DCP, Xinzhongcun Chemical Industry Co., Ltd. 13) nk Ester A-200, Xinzhongcun Chemical Industry Co., Ltd. 14) NK Ester A-400, Xinzhongcun Chemical Industry Co., Ltd. 15) RIMTEC The VC843 is made of a crosslinking agent having two or more polymerizable unsaturated bonds and a half-life temperature of 1 3 5 to 200. (Example of the polymerizable composition of the organic peroxide-based thermal polymerization initiator): initial release property of the release sheet of 丨~丨3, mold release property after heating, mechanical strength, water repellency and high temperature High discoloration resistance. Polymerization of an organic peroxide-based thermal polymerization initiator which does not contain a crosslinking agent having two or more polymerizable unsaturated bonds and a half-life temperature of 135 to 2 〇〇t> Comparison of the properties of the product W. The thermosetting property of the W丨-36-201238992 The initial mold release property, the water-repellent moldability of the de-linked cyclic olefin resin film after heating, and the horse temperature-resistant discoloration are low.衰湘,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The heat-curable parent-ring thin hydrocarbon resin film of the comparative example 2 obtained in the sample 2 was water-repellent, and the mold release property after heating and the mechanical strength were low. The temperature of the compound m was 135. Oxide 糸...poly & starter, but parental agent with more than 2 polymerizable unsaturated bonds The thermosetting crosslinked cyclic olefin resin of Comparative Example 3 obtained from the polymerizable composition having a too small content is low in water repellency, initial mold release property, mold release property after heating, and high temperature discoloration resistance. The half life of 1 minute is contained. The thermosetting property of Comparative Example 4 obtained by using a polymerizable composition having a temperature of 135 to 20 (TC of an organic peroxide-based thermal polymerization initiator but having a crosslinking agent having two or more polymerizable unsaturated bonds) The bicyclic olefin resin film is brittle and cannot be measured for physical properties. It contains an organic peroxide having a crosslinking agent having two or more polymerizable unsaturated bonds, but not having a one-minute half-life temperature of 135 to 2 〇〇. The thermosetting crosslinked cyclic olefin resin films of Comparative Examples 5 and 6 obtained by the polymerizable composition of the thermal polymerization initiator have low water repellency, mechanical strength, initial mold release property, and mold release property after heating. A thermosetting bond of Comparative Example 7 obtained by using a crosslinking agent having two or more polymerizable unsaturated bonds, but not containing a polymerizable composition of an organic peroxide-based thermal polymerization initiator having a one-minute half-life temperature of 135 to 20 Ot Link The water repellency, initial mold release property, mold release property after heating, and high temperature change resistance of the thin hydrocarbon resin film are low. -37- 201238992 Two crosslinkers having two or more polymerizable unsaturated bonds are used for the half life. Water repellency, initial moldability, and heat-heating of the thermosetting crosslinked cyclic olefin resin film of Comparative Example 9 obtained by a polymerizable composition having a content of 135 to 20 (the organic peroxide-based initiator of rc) The release property and the high-temperature discoloration resistance are low. The half-life temperature of the cross-linking agent containing a cross-linking agent having two or more polymerizable unsaturated bonds is 135 to 20 (the organic peroxide-based starting agent of rc is excessively added). The thermosetting crosslinked cyclic olefin resin which is obtained by comparison with the polymerizable composition is brittle and cannot be measured. A comparative example obtained from a polymerizable composition containing an organic peroxide-based thermal polymerization initiator having a one-minute half-life temperature of 135 to 2 Å containing a crosslinking agent having two or more polymerizable unsaturated bonds The water repellency of the thermosetting crosslinked cyclic olefin resin film is low in the initial release and the release property after heating. Containing a cross-linking agent having two or more polymerizable unsaturated bonds, containing an organic peroxide thermal polymerization initiator having a one-minute half-life temperature of 135 to 200 tons, containing a one-minute half-life temperature lower than 135 〇c machine peroxide heat Comparative Example 4 of the polymerization initiator and the film formation system of the polymerizable composition of the comparative example were impossible. [Industrial Applicability] The thermosetting crosslinked cyclic olefin resin composition of the present invention is applicable to a semiconductor encapsulating step film in the manufacture of a semiconductor device. The method of using the thermosetting crosslinked cyclic olefin resin film of the present invention for semiconductor encapsulation is not particularly limited. The semiconductor package, but the heat polymer 8 and the period off, but the heat polymer.j 10, but the mode of the compound ί3, but the system of the supply of 15 is thin, the specific method of the method -38-201238992 (i) a method of resin-sealing between a lead frame on which a semiconductor wafer is mounted and an inner surface of a metal mold on one side so as to be in contact with the lead frame substrate, and (II) mounting a semiconductor a method of performing a resin sealing by interposing a release film between a semiconductor wafer surface of a lead frame substrate of a wafer and an inner surface of at least one metal mold to fill a sealing material between the wafer and the mold during sealing. The release film is interposed between at least one side of the upper surface of the upper mold and the lower mold. In addition, the thermosetting crosslinked cyclic olefin resin composition t' of the present invention is excellent in water repellency even if it does not contain a fluorine component containing fluorine in a molecule and a polyfluorene-forming knife, and is formed into a semiconductor package. The steps used various molded bodies other than the enamel film. The thermosetting crosslinked cyclic olefin resin of the present invention is suitable for use as a release film for a cover layer attachment step of a printed circuit board and a flexible printed circuit board. [Simple description of the diagram] None. [Main component symbol description] No 0 -39-

Claims (1)

201238992 VII. Patent Application Range: 1. A thermosetting crosslinked cyclic olefin resin composition containing 100 parts by mass of (a) a cyclic olefin monomer and 〇7 to 4 parts by mass of (b) [ In addition to the (a), a crosslinking agent having two or more polymerizable unsaturated bonds, and a (4) i minute half-life temperature (half time sinking 1111^1^111^) of 1.15 to 15 parts by mass is 13S to 20 (rc) The organic peroxide-based thermal polymerization initiator and (d) the polymerizable composition of the ring-opening metathesis polymerization catalyst are heated, ring-opened metathesis polymerization and cross-linking. 2. The heat of the patent application scope a hardenable crosslinked cyclic olefin resin composition, wherein the (a) cyclic olefin single system is a lower alkylene monomer. 3_ The thermosetting crosslinked cyclic olefin resin composition according to the scope of the application, wherein (b) [In addition to the (a), a crosslinking agent having two or more polymerizable unsaturated bonds] is a (meth)acrylic acid vinegar having two or more polymerizable unsaturated bonds. a thermosetting crosslinked cyclic olefin resin composition of the range 1 of which d) a ring-opening metathesis polymerization catalyst ruthenium carbene complex. 5. A thermosetting crosslinked cyclic olefin resin film which is a thermosetting crosslinked ring as claimed in claim 1 6. The olefin resin composition is composed of 6. The thermosetting crosslinked cyclic olefin resin film of claim 5 is a release film used in the semiconductor packaging step. 7. The thermosetting hardening agent according to claim 5 A cyclic olefin resin film which is a release film for producing a printed circuit board. -40 - 201238992 A method for producing a thermosetting crosslinked cyclic olefin tree composition according to the scope of the patent application, which contains 1 〇〇 parts by mass of u) a cyclic olefin monomer, 0. 7 to 40 parts by mass of (b) [except for the 'crosslinker having two or more polymerizable unsaturated bonds'), 1.1 5 to 丄$ The mass fraction of (c) l minute half-life temperature is 135~2 〇 (rc organic peroxide-based thermal polymerization initiator and (d) open-loop metathesis polymerization catalyst polymerizable composition heating, ring-opening metathesis polymerization and Steps for cross-linking. 9. If applying A method for producing a thermosetting crosslinked cyclic olefin resin composition according to the invention, wherein the (a) cyclic olefin single system norbornene-based monomer. 10. The thermosetting cross-linking according to claim 8 In the method for producing a cyclic olefin resin composition, the (b) [crosslinking agent having two or more polymerizable unsaturated bonds in addition to the (a)) has two or more polymerizable unsaturated bonds (曱) The method for producing a thermosetting crosslinked cyclic olefin resin composition according to any one of claims 8 to 10, wherein the ring-opening metathesis polymerization catalyst is ruthenium carbene Things. 12. A method for producing a thermosetting crosslinked cyclic olefin resin film according to claim 5, which comprises a cyclic olefin monomer containing ruthenium by mass, and 0.7 to 40 parts by mass of (b) [In addition to the (a), a crosslinking agent having two or more polymerizable unsaturated bonds], and (c) one minute half-life temperature of 丨丨5 to 丨5 parts by mass is 135 to 2 〇〇 <> The organic peroxide-based thermal polymerization initiator and (d) the polymerizable composition of the ring-opening metathesis polymerization catalyst are coated on the support, and the steps of heating, ring-opening metathesis polymerization and crosslinking on the support are carried out. . -41 - 201238992 1 3 ·If the scope of application is patented How to make a film Monomer. 12 items of '', hardened cross-linked cyclic olefin resin Ί-like dilute hydrocarbon single system 降 olefin system 14 · as claimed in the scope of patent 1-2, 丄 丄 、, 更 父 父 父 、 In the method for producing a resin film, the (b) [crosslinker having two or more polymerizable unsaturated bonds in addition to the (a)] is a (fluorenyl) acrylate having two or more polymerizable unsaturated bonds. . The method for producing a thermosetting crosslinked cyclic olefin resin film according to any one of claims 12 to 14, wherein the (d) ring-opening metathesis polymerization catalyst is a ruthenium carbene complex. I -42- 201238992 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: