WO2002098974A1

WO2002098974A1 - Resin composition, prepreg, and layered product

Info

Publication number: WO2002098974A1
Application number: PCT/JP2002/005352
Authority: WO
Inventors: Hitomi Takeuchi; Hitoshi Shimizu; Fumio Takano
Original assignee: Zeon Corporation
Priority date: 2001-06-01
Filing date: 2002-05-31
Publication date: 2002-12-12
Also published as: JP2002363370A; JP4581292B2

Abstract

A curable resin composition comprising 100 parts by weight of an alicyclic olefin polymer ingredient and 10 to 90 parts by weight of a thermosetting ingredient, characterized in that (1) at least one of the polymers constituting the alicyclic olefin polymer ingredient has polar groups and (2) at least one of the polymers constituting the alicyclic olefin polymer ingredient has a weight-average molecular weight Mw of 5,000 to 50,000, excluding 50,000.

Description

Description Resin composition, pre-preda and laminate

The present invention relates to a curable resin composition, a prepreg impregnated with the composition, and a laminate using the same. Background art

In order to reduce the size and weight of electronic devices and increase their density, a method is used in which electronic components (leadless chip components) are surface-mounted on printed circuit boards. In order to increase the circuit density of printed circuit boards, multilayer printed circuit boards, in which the insulating layers of the printed circuit board are made into multiple layers and the circuits are arranged in the inner layers, have been increasingly used. In addition, in order to effectively use the area of the circuit board, electrical connection between inner circuits arranged via an insulating layer has been made through non-through holes.

As a material for forming the insulating layer of such a high-density multilayer printed circuit board, a fiber base material such as a glass fiber nonwoven fabric or an aromatic polyamide fiber (aramid fiber) nonwoven fabric is impregnated with a resin. Pre-preda has been proposed. When the viscosity of a resin composition (varnish) containing a resin and a solvent is high, it is necessary to make a prepreg with a low solid content concentration. As a result, air bubbles remain in the pre-predator, and furthermore, the air bubbles cannot be extruded due to poor fluidity during molding, and air bubbles remain in the laminated body. When a printed wiring board is manufactured using such a laminate, the plating liquid may penetrate into the bubbles, causing insulation failure and reducing the electrical reliability in some cases.

At present, in the production of prepreg, epoxy resin is used to impregnate the fiber base A xy resin is generally used. Epoxy resins are characterized by low viscosity even at high solids concentrations and high fluidity even during semi-curing. By using this epoxy resin, it is possible to extrude the air bubbles remaining in the pre-predder at the time of pressure molding, and it is possible to obtain a laminate having few residual air bubbles.

On the other hand, with further densification, the laminates are required to have improved electrical properties such as dielectric constant. In order to meet this demand, it has been proposed to use a curable resin composition comprising an alicyclic olefin polymer and a thermosetting component (International Publication WO98 / 15595). By using this resin composition, a laminate having a low dielectric constant and a low water absorption, and having high solder resistance and delamination strength can be obtained. Disclosure of the invention

By the way, in the examples of the above publication, as the alicyclic olefin polymer, a polymer having no polar group having a relatively low weight average molecular weight Mw, or a polymer having a weight average molecular weight of

5 0 0 0 0 or more, however _c to obtain a curable resin composition using a polymer with polar groups, when the present inventors further investigated, alicyclic Orefuin polymer, (1) a polar A varnish of a curable resin composition using only a polymer having no group has insufficient impregnation into a fiber base material. (2) A varnish having a polar group having a weight average molecular weight of 500 000 or more. Since the varnish of the curable resin composition containing the coalesced substance had a high viscosity and tended to decrease the fluidity, it was found that there was a problem of residual air bubbles.

Accordingly, an object of the present invention is to provide a curable resin composition comprising an alicyclic olefin polymer and a thermosetting component and having good impregnation and fluidity, a prepreg impregnated with the same and a prepreg manufactured using the prepreg. An object of the present invention is to provide a laminate having few bubbles. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the use of an alicyclic olefin polymer having a polar group having a relatively low weight-average molecular weight Mw can improve impregnation and fluidity. The present inventors have found that it is possible to obtain a laminate having a small amount of residual air bubbles, and based on this finding, have completed the present invention. Thus, according to the present invention, as a first invention, a curable resin composition containing 100 parts by weight of an alicyclic olefin polymer component and 10 to 90 parts by weight of a thermosetting component is provided. (1) at least one of the component polymers constituting the alicyclic olefin polymer component has a polar group; and (2) the component polymer constituting the alicyclic olefin polymer component. At least one of the curable resin compositions is characterized in that the weight average molecular weight Mw is at least 50,000 and less than 50,000, and as a second invention, a fiber base material is provided. A prepreg impregnated with the curable resin composition is provided. As a third invention, a laminate having a layer obtained by curing the prepreg is provided. BEST MODE FOR CARRYING OUT THE INVENTION

(Curable resin composition)

The curable resin composition of the present invention contains an alicyclic olefin polymer component and a thermosetting component.

In the present invention, the alicyclic olefin polymer component is composed of one or more alicyclic olefin polymers (component polymers).

The alicyclic olefin polymer according to the present invention comprises a polymer containing a repeating unit derived from an olefin having an alicyclic structure (hereinafter, also referred to as an alicyclic olefin).

Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. From the viewpoints of mechanical strength, heat resistance, and the like, a cycloalkyne structure is preferable. In addition, alicyclic structures can be monocyclic or polycyclic (condensed polycyclic, bridged, , Etc.). Although there is no particular limitation on the number of carbon atoms constituting the alicyclic structure, when the number is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15, Various properties such as strength, heat resistance and moldability are highly balanced and suitable. The proportion of the repeating unit derived from the olefin having such alicyclic structure in the alicyclic olefin polymer is appropriately selected according to the purpose of use, but is usually 30 to 100% by weight, preferably 50 to 100% by weight. It is 100% by weight, more preferably 70 to 100% by weight. If the proportion of the repeating unit derived from an alicyclic olefin is too small, heat resistance, dielectric properties, and low water absorption are unfavorably poor.

In the present invention, one of the component polymers constituting the alicyclic olefin polymer component is an alicyclic olefin polymer having a polar group.

Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Carboxyl groups or carboxylic anhydride groups are preferred. These polar groups can be used alone or in combination of two or more. The content of the polar group in the alicyclic olefin polymer component is appropriately selected depending on the purpose of use, but it is usually determined with respect to all the repeating units of all the component polymers constituting the alicyclic olefin polymer component. 3-1 5 0 mole ^_0/0, preferably from 6 1 0 0 mole ^_0/0, more preferably 1 0-8 0 mol% Dearu. When the content of the polar group of the alicyclic olefin polymer is within this range, the property of impregnating the fiber base material is excellent, and the properties of adhesion, heat resistance and low water absorption are highly balanced, which is preferable.

When two or more alicyclic olefin polymers are used as component polymers, not all alicyclic olefin polymers need to have a polar group, but all alicyclic olefin polymers are polar. Having a group is preferable because higher impregnation can be obtained. Cycloaliphatic olefin polymers are usually polymerized by addition or ring-opening polymerization of alicyclic olefins and, if necessary, hydrogenation of unsaturated bonds, or addition polymerization of aromatic olefins. Then, it is obtained by hydrogenating the aromatic ring portion of the polymer.

The alicyclic olefin polymer having a polar group includes, for example, 1) a polar group-containing compound by introducing a compound having a polar group into the alicyclic olefin polymer through a modification reaction. By (co) polymerizing a monomer as a polymerization component, or 3) (co) polymerization using a monomer containing a polar group such as an ester group as a polymerization component, and then hydrolyzing the ester group It is obtained by doing. Among these, a polar group-containing alicyclic olefin polymer obtained by the method 1) is preferred.

Examples of the alicyclic olefin used to obtain the alicyclic olefin polymer include bicyclo [2.2.1] hepta-12-ene (common name norbornane), 5-methyl-bicyclo [2 2.1) Hepta-2-ene, 5,5-dimethyl-1-bicyclo [2.2.1] Hepter 2-ene, 5-ethyl-bicyclo [2.2.1] Hepta-2-ene , 5-butyl-bicyclo [2.2.1] hepta-2-ene, 5-ethylidene-bicyclo [2.2.1]-hepta-2-ene, 5-hexyl-bicyclo [2 2. 1] Hepta_2_5, 5-Octyl-1-bicyclo [2.2.1] Hepter2_5, 5-octadecyl-bicyclo [2.2.1] Hepta1-2-cyclo , 5-ethylidene-bicyclo [2.2.1] hepter 2--, 5-methylidene-bicyclo [2.2.1] hepter 2--, 5-vinylinobicyclo [2.2.1] Hepta 1—2, 5—Pro Norre one bicyclo [2.2.1] Heputa 2 E down, tricyclo ^{^{[4. 3. 0. I 2 '5}} ] dec-one 3,7-diene (common name dicyclopentadiene), tricyclo [4. 4, 0 · 1 ² ' ⁵ ] pen power 3, 8-gen, tricyclo [4 · 4.0. 1 ² ' ⁵ ] pen power 3-ene, 5-pen mouth pentyl-one mouth [2. 2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenylene Rubishikuro [2.2.1] hept-one 2-E down, Te preparative Rashikuro [4.4.1 0.1 ² ^'5 1 ^{^7-10.]} - de de force one 3- E down (just Te tiger Sik opening dodecene Tomore, U), 8-Mechirute Torashikuro [4. 4. 0.1 ² '5. 17.1 0] - Dodeka 3-E down, 8-Echirute Torashikuro [4. 4. 0. ^{^{^{^{I 2 '5 1 7 · 1}}}} °] -. de de force one 3-E down, 8- Mechiridente Torashikuro ^{^{[4. 4. 0. I 2' 5}} 1 7 '10] -. Dodeka 3 E down, 8 - Echiridente Torashikuro [4.4.1 0.1 ² ^'5 1 ^7.' ¹ °] -. de de force one 3-E down, 8- Byurute Torashiku port [4.4.1 0.1 ² ^'5 1 ⁷ ^'10] - Dodeka 3 E down, 8- Purobe two Rute Torashi black ^{^{[4. 4. 0. I 2' 5}} I 7 · 10] -. dodeca one 3-E down, 8- consequent Ropen Chirute Torashikuro ^{^{[4. 4. 0. I 2 '5}} . 1 7' 1. ] -. De de force one 3-E down, Kishirute Torashikuro to 8-Sik opening [4. 4. 0.1 ² - ⁵ 1 ⁷ ^'1. - de de car 3 E down, to 8 consequent opening Kiseninore Ichite Torashikuro ^{^{[4. 4. 0. I 2 '5}} 1 7 · 1 °] -. De de force one 3-E down, 8- phenyl one consequent opening Penchirute Torashiku port ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] - Dodeka 3 E emissions; tetracyclo ^{[. 7. 4. 0. 1 1 °} · 13 0 2 '7] trideca 1,2,4,6,11—Tetraene (only 1,4-methano-1,4,4a, 9a—Tetrahydrofluorene), Tetracyclo [8.4.0.I ^{1 1} '. ¹⁴ 0 ^3' ^8] te Toradeka one 3, 5, 7, 1 2 Te Toraen (simply 1, 4-methano one 1, 4, 4 a, 5 , 10, 1 0 a - to Kisahi mud both anthracene intends Rere), pentacyclo ^{^{[6. 5. I 3 '6.}} ◦ 2' 7. 09. 1 3] Pentazaka 3, 10-Zhen, pentacyclo ^{^{[7. 4. 0. I 3 '6}} . I 10' ^13.0 ² ^'7] pentadeca _ 4, 1 1-Jen, tetramer or more adducts of Shikurobe Ntajen, 5 _ Hue sulfonyl Cyclo [2.2.2].] To Puto 2 E down, Te Torashikuro [6.5.1 0.1 ² ⁵ '. 0 ⁸ - ^{1 3]} trideca one 3, 8, 1 0, 1 2-te Toraen (Simply 1,4—Methane 1,4,4a, 9 Both a- Te Torahi mud fluorene intends Rere), Te Torashikuro ^{^{[6. 6. 0. I 2 '5}} . 0 8' 13] Tetoradeka 3, 8, 1 0, 1 2 Tetoraen (simply 1, 4 one methano one 1, 4, 4a, 5, 10 and 10a—also known as hexahydroanthracene),

5-Methoxy-1-carbonyl-1-bicyclo [2.2.1] hepta-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] Hepta-2-ene; 5-Methoxycarboninolebicyclo [2.2.1] Heptol 2-ene, 5_ethoxycarbonyl-bicyclo [2.2.1] Hept-1-ene 2-ene, 5-methyl-5-methoxycanolebonylbicyclo [2.2.1] heptone 2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] heptone 2_en, bicyclo [2.2.1] hept-1-5-enyl-1 2-methylpropionate, bicyclo [2.2.1] heptoto 5-enyl-1 2-methylotatanate, bisik [2.2] [1] hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5,6-di (hydr Roxymethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy i-propinolebicyclo [2.2.1] hept-2-en, 5, 6-dicarboxy bicyclo [2 2. 1] Heptot-2-ene; 5-Cyanobicyclo [2.2.1] Hept-12-, bicyclo [2.2.1] Hept-12-ene-5, 6-dicarboxylic acid Mi de, 8 main butoxycarbonyl Te Torashikuro [4.4.1 0.1 ² ^'5 1 ^{^7-10.]} - de de force one 3-E down, 8-methyl-8-main Tokishikarubo two Norete Torashikuro [4. ^{^{^{4. 0. I 2 '5 1 7}}} 1 °] -. Dodeka 3 E down, 8-arsenide Dorokishimechirute Torashikuro ^{^{[4. 4. 0. 1 2' 5}} 1 7 · 1 °] -. de de force one 3 _ E down, 8- Karubokishite Torashikuro ^{^{[4. 4. 0. I 2 '5}} 1 7.' 1 °] - norbornene monomer, such as de de force one 3-E down; cyclobutene, Shikuropen Ten, cyclo Hexene, 3,4-dimethylcyclope Content, 3-methylsic Mouthhexene, 2- (2-methylbutyl) 1-1-cyclohexene, cyclootaten, 3a, 5,6,7a-tetrahydro-1,4,7-methano 1H-indene, such as cycloheptene Monocyclic cycloalkene-based monomers; Biercyclohexene and Bürsik-mouth hexane; Bul-based alicyclic hydrocarbon-based monomers; alicyclic conjugated-based monomers such as cyclopentadiene and cyclohexadiene And the like.

Examples of the aromatic olefin include styrene, α-methylstyrene, dibutylbenzene and the like.

The alicyclic or aromatic olefins can be used alone or in combination of two or more.

The method for polymerizing alicyclic olefins and aromatic olefins and the method for hydrogenation as required are not particularly limited, and can be performed according to known methods.

In the present invention, one of the component polymers constituting the alicyclic olefin polymer component has a weight average molecular weight Mw (hereinafter, may be simply referred to as Mw) of 500 to 5,000. Preferably, it is an alicyclic polymer having a molecular weight of 5,000 or more and 4,000 or less. Of course, the alicyclic olefin polymer having Mw of 5,000 or more and less than 50,000, preferably 5,000 or more and 4,000 or less simultaneously has the polar group described in detail above. May be present, or an alicyclic olefin polymer different from the alicyclic olefin polymer having a polar group.

The weight average molecular weight is a weight average molecular weight in terms of polystyrene (or polyisoprene) measured by gel permeation chromatography (GPC) using chloroform or tetrahydrofuran as a solvent. Normally, porcine form is used for Mw measurement of a polymer having no polar group, and tetrahydrofuran is used for Mw measurement of a polymer having a polar group.

When the amount of the polymer ある whose M w is 500 or more and less than 500 It is usually at least 10% by weight, preferably 20 to 100% by weight, based on the total amount of all the component polymers constituting the olefin polymer component. / ₀ , more preferably 20 to 90% by weight, the formation of bubbles can be suppressed.

The alicyclic olefin polymer component according to the present invention includes, in addition to the polymer having Mw in the above-described range, for example, a polymer having Mw of 500 or more and less than 900 ° An alicyclic olefin polymer having a relatively high Mw such as ② can be used together.

These polymers having a relatively high Mw are used in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 90% by weight or less, based on the total amount of all the component polymers constituting the alicyclic olefin polymer component. When used in a proportion of 10 to 80% by weight, the formation of bubbles is suppressed, the moldability is excellent, and the mechanical and thermal properties of the laminate are improved.

Further, in the present invention, an alicyclic olefin polymer having an Mw of more than 900, ③ ゃ an alicyclic olefin polymer having an Mw of less than 50,000, an alicyclic olefin polymer component Although it is possible to use as a component polymer constituting the above, from the viewpoint of securing good fluidity, the use ratio is preferably 10% by weight or less, more preferably 10% by weight or less in the alicyclic olefin polymer component. Is less than 5% by weight. As a method for adjusting the Mw of the alicyclic olefin polymer, for example, in the ring-opening polymerization of the alicyclic olefin, a molecular weight modifier such as a bullet compound or a gen compound may be added to the monomer in an amount of 0.1 to 0.1 wt. A method of adding about 1 to 10 mol% can be mentioned. A relatively low Mw polymer can be obtained by using a small amount of the molecular weight modifier, and a relatively low Mw polymer can be obtained by using a large amount. can get.

Examples of the vinyl compound used as a molecular weight modifier include α-olefin compounds such as 1-butene, 1-pentene, 1-hexene, and 1-octene; styrene compounds such as styrene and vinylinoletoluene; ethylbutyl ether and isobutyl Ether compounds such as butyl ether and aryl glycidyl ether; aryl Halogen-containing vinyl compounds such as chloride; oxygen-containing vinyl compounds such as aryl acetate, aryl alcohol and dalicidyl methacrylate; and nitrogen-containing vinyl compounds such as acrylamide. As a gen compound,

Non-conjugated diene compounds such as 1,4-pentagen, 1,5-hexadiene, 1,6-hexadiene, 2-methyl-1,4-pentadiene, 2,5-dimethinolate 1,5-hexadiene; 1 Conjugated compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentagen, and 1,3-hexadiene.

The thermosetting component used in the present invention is composed of a compound that is cured by heating, and may contain a curing agent or a curing accelerator as needed. A compound that cures by heating is a low molecular compound before heating and becomes a polymer by heating, and then cures, but it is a polymer before heating but does not cure at room temperature, but cures by heating. You may. The mechanism of curing by heating is not particularly limited, and examples thereof include a mechanism by a crosslinking reaction and a condensation reaction.

Examples of such a thermosetting component include a thermosetting component containing a compound having two or more reactive groups in one molecule, a curing agent, and a curing accelerator.

Compounds having two or more reactive groups in one molecule include those having two or more epoxy groups in one molecule, those having two or more butyl groups or internal olefin groups in one molecule, Those having two or more (meth) acryloyl groups in the molecule, those having at least two or more reactive groups selected from epoxy group, butyl group, and (meth) acryloyl group in one molecule are exemplified. Of these, those having two or more epoxy groups in one molecule, or at least two or more reactive groups selected from epoxy group, butyl group, and (meth) acryloyl group in one molecule Those having a group are preferred. Furthermore, in one molecule, at least two or more selected from epoxy groups, vinyl groups, and (meth) atalyloyl groups Of those having the above reactive group, those in which at least one of the reactive groups is an epoxy group are particularly preferred.

Examples of the compound having two or more epoxy groups in one molecule include epoxy such as bisphenol type, novolak type, alicyclic type, heterocyclic type, condensed type, glycerin type and dicyclopentadiene type. Compounds. Specifically, a bisphenol type epoxy compound represented by the formula (E 1), a hydrogenated bisphenol type epoxy compound obtained by hydrogenating a bisphenol type epoxy compound represented by the formula (E 1), a compound represented by the formula (E 2) And the like.

(In the formula, R is a hydrocarbon group, n = 0 or an integer of 1 or more. However, R may be a straight chain or branched, but is preferably an isopropylidene group. Further, n is 0 or It may be a mixture of integers greater than or equal to 1. Further, the aromatic ring may be substituted with a halogen group.)

(In the formula, R is a hydrocarbon group, n = 0 or an integer of 1 or more. However, R may be a straight chain or branched, but is preferably an isopropylidene group. Further, n is 0. Or a mixture of integers greater than or equal to 1. n = an integer from 0 to 5)

Among those having at least two or more reactive groups selected from an epoxy group, a vinyl group, and a (meth) acryloyl group in one molecule, at least one of them has a reactive group. Examples of the oxy group include a buridyl compound having a daricidyl group and a (meth) atalylate compound, a bur compound having a cyclohexenoxide structure, and a (meth) atalylate compound. More specifically, 4-vinyl-1- 1-cyclohexene 1,2-epoxide, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxy-11-butene, 1,2-epoxy Examples thereof include 1-5-hexene, 1-aryl-1,3,5-diglycidyl isocyanurate, and 1,3-diallyl-5-glycidyl isocyanurate.

Polyimide can be used as a compound having two or more reactive groups in one molecule. More specifically, addition-type aromatic polyimides such as nadic acid-terminated polyimides and acetylene-terminated polyimides; polyaminobismaleimide (PI) resins, epoxy resins, acryl compounds, acryl compounds, and bur compounds on PI resins And modified bismaleimide-type polyimides such as bismaleimide 'triazine (BT) resin. These compounds having two or more reactive groups in one molecule can be used alone or in combination of two or more.

Examples of the curing agent include an aliphatic polyamine compound, an alicyclic polyamine compound, an aromatic polyamine compound, a bisazide compound, an acid anhydride, a dicarboxylic acid compound, a diol compound, a triol compound, a polyvalent phenol compound, a polyamide, and a diisocyanate compound. And preferably polyhydric phenol compounds and aromatic polyamine compounds, specifically, phenol novolak, tarezol novolak, diaminodiphenylmethane dicyandiamide and the like. These curing agents can be used alone or in combination of two or more. The amount of the curing agent is usually 0.01 to 20 parts by weight based on 100 parts by weight of the compound having two or more reactive groups in one molecule.

Examples of the curing accelerator include amine compounds, imidazole compounds, Known compounds such as a nitrogen-containing heterocyclic compound such as diazabicycloundecene, an organic phosphine, an organic boron complex, a quaternary ammonium compound, and a quaternary phosphonium can be used. Of these, imidazole compounds are preferred because they have a high curing promoting effect, and organic phosphorus compounds and diazabicycloundecene are effective in reducing the extraction of ionic impurities.

Examples of the imidazole-based compounds include 2-methylimidazole, 2-ethylimidazole, 2-ethynole 4-methinoleimidazole, bis-1-ethynole-4-methylimidazole, 1-methyl-2-ethylimidazole, 2 —Alkyl-substituted imidazole compounds such as isopyl pyrimidazole, 2,4-dimethylimidazole, and 2-heptadecylimidazole; 2-phenylimidazole, 2-phenylimidazole 4-methinoreimidazole, 1-benzyl_2-methylimidazolone, 1—Benzizole 2—Echinoleimidazonole, 1—Benzyl 2—Feninolei midazonole, Benzi midazonole, 2-Echinole-1-4-methinole 1- (2′—Cyanoethyl) imidazole, 2-Ethyru-4-methyl-1— 2, one (3 ", 5" —diamino triage Le) ethyl) Imidazole compounds such as imidazole and the like. Imidazole compounds substituted with a hydrocarbon group containing a ring structure such as an aralkyl group, 2,4'-diamino-6- [2'-ethyl-4'-methylimidazolyl (1) ')] Ethyl-s-triazine, 2-methylimidazole-isosocyanuric acid adduct, 2-methylimidazole-trimeritic acid adduct, 2-pindecylimidazole, 1-cyanoethyl-2-pindecylimidazole, 2,4 —Diamino-1 6— [2 '—Pindecylimidazolyl — (! _')] Ethyl- _s — Triazine and the like. Examples of the organic phosphorus compound include triphenylphosphine and triphenylphosphine phenol salt. Among these, imidazole having a substituent having a ring structure is preferred from the viewpoint of compatibility with the alicyclic olefin polymer, and 1-benzyl-12-phenylimidazole is particularly preferred. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator can be appropriately selected according to the type of the compound having two or more reactive groups in one molecule.

The amount of the thermosetting component is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the alicyclic olefin polymer component. When it is in this range, the moldability is good and the physical properties such as heat resistance are excellent, so that it is preferable.

In addition to the above, the thermosetting resin composition of the present invention includes a radical crosslinking agent, a flame retardant, another resin, a filler, a heat-resistant stabilizer, a weather-resistant stabilizer, a leveling agent, an antistatic agent, and a slurry. Agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, emulsions, etc., and the mixing ratio is within a range that does not impair the object of the present invention. It is appropriately selected.

Examples of the radical cross-linking agent include methyl ethyl ketone peroxide, cyclohexanone pentanoloxide, 1,1-bis (t-butynoleperoxy) -13,3,5-trimethylcyclohexane , 2,2-Bis (t-butylperoxy) butane, t-butylhydridoperoxide, 2,5-dimethylhexane-1,2,5-dihydrazinoleoxide, dicumylphenoloxide, 2,5-dimethinole-1,2,5 - di (t _ Buchiruperuokishi) - 3 - to relaxin, alpha, alpha-bis (t one Buchiruperuokishi _ _m - isopropyl) benzene, OTA Tano I le peroxide O, dimethylsulfoxide, isobutyryl peroxide O, dimethylsulfoxide, pel O carboxymethyl dicarbonate And other organic peroxides.

These crosslinking agents can be used alone or in combination of two or more, and the amount thereof is usually 0.01 to 0.1 part by weight of the alicyclic olefin polymer component. -20 parts by weight, preferably 0.01-1 parts by weight.

As the flame retardant, a flame retardant generally used to make plastics flame retardant can be used, and a reactive flame retardant can also be used. Concrete Phosphoric esters such as tris (tribromoneopentyl) phosphate, modifiphenyl ether, antimony trioxide, 9,10-dihydro 9-oxa 10 10-phosphaphenanthrene 1 1 0-oxide and its quinone adduct, polyphosphamide, melamine polyphosphate, tetrabromobisphenol A and the like.

The blending amount of the flame retardant is appropriately selected according to the purpose of use, but it is usually 0.1 to 50 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of the cyclic cyclic polymer component. 0 parts by weight is preferably employed.

Examples of the polymer other than the alicyclic olefin polymer component and the thermosetting component include a rubbery polymer and other resins.

The rubbery polymer is a polymer having a Tg of usually 30 ° C or less, and specific examples include natural rubber, polyisobutylene rubber, butyl rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile 'butadiene. Copolymer rubber, styrene. Butadiene copolymer rubber, styrene ■ Gen-based rubber such as isoprene copolymer rubber, styrene. Butadiene. Isoprene terpolymer rubber, and hydrogenated products of these gen-based rubbers; Saturated polyolefin rubbers such as ethylene propylene copolymers and other ethylene-α-olefin copolymers, propylene and other α-olefin copolymers; ethylene propylene- gen copolymers, and olefin copolymers , Α-olefin 'isoprene copolymer, isobutylene'gen copolymer, iso- Polyolefin-based polymer rubber such as Tylene 'isoprene copolymer; special rubber such as urethane rubber, polyether rubber, acrylic rubber, propylene oxide rubber, ethylene acrylic rubber; styrene-butadiene-styrene block copolymer rubber Styrene-based thermoplastic elastomers such as styrene-isoprene-styrene block copolymer rubber and hydrogenated products thereof; urethane-based thermoplastic elastomers 1; polyamide-based thermoplastic elastomers; 1,2-polybutadiene-based Thermoplastic Sex elastomers; and the like.

Other resins include, for example, polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene; polyamides such as nylon 66 An ethylene-ethyl acrylate copolymer, an ethylene-butyl acetate copolymer; a polyester; a polycarbonate; an ataryl resin; and a polyimide.

These polymers can be used alone or in combination of two or more. The mixing ratio of the other polymer is usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the alicyclic olefin polymer component. 0 parts by weight. The filler can be blended for the purpose of improving the mechanical strength, reducing the coefficient of thermal expansion, and obtaining an arbitrary dielectric constant. Specifically, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbide, silicon carbide, boron nitride, beryllia, magnesia, zirconia, forsterite, steatite, spinel, mullite, titania , calcium titanate, titanium phosphate burrs © beam, titanium Sanz strontium, titanate burrs Umusu _{_{strontium, B i 4 T i 3 0}} 12 - P b T i 0 3 system, B i ₂ W_〇 ₆ - B i ₂ MO0 ₆ _{system, P b (F e 2/} 3 W 1/3) 0 3 -P b (F e 1/2 Nb 1/2) 0 3 _{system, P b (Mg 1/3 N b} 2/3) Well-known inorganic fillers such as O ₃ -PbTio_3_MgO system can be used. The shape is selected from powder, granule, needle, and fiber depending on the purpose.

The compounding amount of the filler is in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer component, and the compounding amount is determined according to the purpose. (Varnish)

The varnish of the present invention is obtained by dissolving the curable resin composition in a solvent. This penis is suitable for impregnating the fiber base material with the curable resin composition. An organic solvent is preferable as a solvent used for preparing the varnish, and in particular, by using a mixed solvent composed of a non-polar organic solvent and a polar organic solvent, excellent impregnation into a fiber substrate is achieved, and dielectric properties are improved. Low water absorption, interlayer adhesion and moldability are highly balanced. When a single organic solvent is used, the curable resin composition may not be sufficiently uniformly dispersed in the fiber base material, and may not cover the fiber interface. As a result, in particular, low water absorption and low dielectric loss tangent are inferior.

Non-polar organic solvents include, for example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene; linear aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; cyclopentane, cyclohexane and the like Of these, aromatic hydrocarbons and alicyclic hydrocarbons, specifically, xylene and toluene, are preferred from the viewpoint of excellent compatibility with the alicyclic olefin polymer. preferable.

Examples of polar organic solvents include halogenated hydrocarbons such as benzene, dichlorobenzene, and the like; ketones such as acetone, methylethylketone, methylisobutynoleketone, cyclopentanone, cyclohexanone, benzophenone, and acetophenone; Ethers such as trahydrofuran, tetrahydropyran and anisol; methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, Esters such as ethyl butyrate, butyl butyrate, amyl butyrate, ethyl lactate, dimethyl carbonate, dimethyl phthalate, methyl phthalate, and γ-butyl lactone; ethylene carbonate, propylene carbonate, etc. Carbonate compounds: Ν-methylpyrrolidone, Ν_ethylpyrrolidone, Ν-phenylpyrrolidone, Ν-benzylpyrrolidone, Ν, ジメチル -dimethylformamide, ,, Ν-dimethylformamide, Ν, Ν-dimethylylacetate Amide compounds such as toamide; nitrile compounds such as acetonitrile, propionitrile, butyronitrile, benzonitrile, and forcepronitrile; Sulfoxide compounds such as dimethyl sulfoxide; and the like. Among these, ketones, esters, carbonate compounds, amide compounds and the like are preferable from the viewpoint of compatibility with the alicyclic olefin polymer, and ketones are particularly preferable, and cyclopentanone and cyclohexanone such as cyclopentanone are preferable. Alkanone is particularly preferred.

The mixing ratio of the nonpolar solvent and the polar solvent can be appropriately selected, but is usually 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably by weight. Is in the range of 20:80 to 80:20.

There is no particular limitation on the amount of the solvent used, but if a varnish is prepared to obtain a prepredder, the solid content concentration is usually 5 to 70% by weight, preferably 10 to 65% by weight, Preferably, the solvent is used in an amount of 20 to 60% by weight.

The method of dissolving the alicyclic olefin polymer component, the thermosetting component, and other components added as needed in a solvent may be in accordance with a conventional method, for example, using a stirrer and a magnetic stirrer. Stirring, high-speed homogenizer, dispurgeon, planetary stirrer, twin-screw stirrer, ball mill, three-roll method, etc. can be used.

(Pre-Preda)

The prepredder of the present invention is obtained by impregnating a fiber base material with the curable resin composition of the present invention.

As the fiber base material relating to the pre-preda of the present invention, those conventionally known for use in the pre-preda can be mentioned. The fibers constituting the fiber base material include polyester fibers, nylon 66 fibers, and aramide fibers (m-phenylene isophthalamide fiber, p—phenylene terephthalamide fiber, p—diphenyl ether terephthalamide fiber, and poly (ethylene terephthalamide) fiber. Organic synthetic fibers such as atalylate fibers); natural fibers such as cellulose, cotton, hemp, wool, and silk; glass fibers (E glass, C glass, D glass, S glass, NE glass, H glass, etc.), asbestos, and inorganic fibers such as carbon fibers. These fibers are individually formed or mixed to form a nonwoven or woven fabric. Among these fibers, preferred are aramide fibers, polyester fibers and glass fibers, and particularly preferred are meta-based amide fibers, para-based amide fibers, wholly aromatic polyester fibers, E-glass fibers, and H-glass fibers. Can be used as it is, but it is preferable to use a surface-treated one for the purpose of improving the adhesion to the curable resin composition. Surface treatment methods include, for example, heat treatment with hot air, infrared light, near infrared light, etc .; immersion treatment with a solvent such as acid, alkali, alcohol, etc .; plasma treatment; corona treatment; ozone treatment; polyimide siloxane, aramide elastomer. First, pre-impregnation treatment with biphenyl type epoxy resin, naphthalene type epoxy resin, coupling agent and the like can be mentioned. These surface treatments can be used alone or in combination of two or more.

Among these surface treatments, a heat treatment or a pre-impregnation treatment with a coupling agent is effective for preventing swelling of the substrate.

In the heat treatment, the fiber substrate is 100-450. C, preferably in a high temperature atmosphere of 140 to 400 ° C. for heating. The heating time can be appropriately selected, and is usually 5 to 120 minutes. By performing the heat treatment under reduced pressure, the heating temperature can be lowered and the heating time can be shortened.

Examples of the coupling agent used in the pre-impregnation treatment include epoxy silane, amino silane, acryl silane, butyl silane, γ-mercaptopropyl trimethoxy silane, and the like. Specifically, butyl trimethoxy silane, vinyl phenyl trimethoxy silane, 3-meta-loxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, 3-aminopropyltrimethoxysilane, Ν— 2- (Aminoechiru) one ₃ - § Mino Pro built Increment Tokishishiran, N-beta (New

-Vinylbenzylaminoethyl) -y-aminopropyltrimethoxysilane,

3-silane capping agents such as 3-mercaptopropyl trimethoxysilane, imidazole silane, triazine silane, etc .; isopropyl trisisostea porphyltitanate, isopropyl isopropyl tris i-dodecylbenzenesulfonyl titanate, isopropyl tris-n-dodecyl Benzenesulfonyl titanate, Isopropyl tris (dioctyl pyrophosphate) titanate, Tetraisopropyl monobis (dioctyl phosphate) titanate, Tetraoctyl monobis (ditridecyl phosphite) Titanate, Tetra ( 2,2-diaryloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophos) Ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylyso stear mouth titanate, isopropyl isostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tritamyl phenyl titanate, isopropyl tri (N —Aminoethyl) titanate coupling agents such as titanate, diphenyloxyacetate titanate, disostearoylethylene titanate; zirconate coupling agents such as acetate alkoxyaluminum disopropylate; zirconia Aluminum-based coupling agents; organopolysilanes, titanium-based adhesion promoters, surface-active coupling agents, and the like.

The amount of the curable resin composition impregnated into the fiber base material is appropriately selected depending on the purpose of use, and is usually 10: by weight ratio of [curable resin composition solids]: [fiber base material]. The range is from 90 to 90: 10, preferably 20: 80 to 80: 20, and more preferably 30: 70 to 70: 30. When it is in this range, the moldability is good, and the dielectric properties, low water absorption and delamination strength are highly balanced, which is preferable. There is no particular limitation on the method for impregnating the fiber base material with the curable resin composition.For example, a method in which the fiber base material is immersed in a varnish of the composition and then the solvent is removed; A method of removing the solvent after flowing the composition into the material, a method of spraying the composition onto a fiber base material, and then removing the solvent are exemplified. The method of removing the solvent is appropriately selected according to the type of the solvent used, but the drying temperature is usually set to 50 to 200 ° C, preferably 70 to 150 ° C. The curable resin composition impregnated into the fiber base material after removing the solvent is preferably in an uncured state. Thereafter, in order to cure the pre-preda, the curable resin composition is heated to a temperature at which a curing reaction occurs.

The thickness of the pre-preda is appropriately selected according to the purpose of use, but is usually from 10 to 100 μm, preferably from 20 to 500 μπι, and more preferably from 50 to 250 μm. Range. When the thickness of the pre-preda is in this range, the mechanical strength and the additivity are balanced, which is preferable.

(Laminate)

The laminate of the present invention is obtained by laminating a plurality of the pre-preda of the present invention, molding under heat and pressure, curing and heat-sealing.

For example, a circuit board can be obtained by laminating a conductor layer made of metal foil or the like on the prepreg of the present invention and then forming a circuit by surface etching or the like. After the circuit board is formed, the metal foil and pre-preda are stacked, heated and pressed, and the surface is etched to form a multilayer circuit board with a conductor layer not only on the outer surface of the laminate but also on the inside. Obtainable. In addition, IC chips and the like can be enclosed and sealed between layers. The method of laminating the conductor layer is not particularly limited. In addition to the method of performing the etching treatment after laminating the metal foil described above, a wet method such as a dry plating such as vapor deposition or sputtering, an electrolytic plating, or an electroless plating is used. There is a method using a method such as a method. The metals commonly used for conductor layers are copper, nickel, tin, silver, gold, aluminum, platinum, titanium, zinc and Chromium and the like. Of these, copper is preferred.

The heating temperature at the time of heating and pressurizing is in the range of 100 to 300 ° C, preferably 150 to 260 ° C. Within this range, the warpage of the laminate can be prevented, and the curing of the curable resin composition can be effectively completed.

When the pressing force at the time of heating and pressurizing is in the range of 10 to 80 Κ§Ζ (: πι ² , preferably 20 to 6 OK gZcm ²⁾ , the pressure between the metal foil and the resin layer, and Adhesion can be increased, and air holes in the fiber base material can be substantially eliminated.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. In the examples, parts and percentages are by weight unless otherwise specified.

(Evaluation method)

(1) The molecular weight was measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

(2) The glass transition temperature (T g) was determined from the peak temperature of the loss tangent of the dynamic viscosity analysis (DMA method).

(3) The moldability was judged by visual observation, `` 〇J '' when there was no white part derived from bubbles, `` △ '' when there was a partial white part, and `` X '' when there was a whole white part. Was evaluated.

(4) The test for delamination strength was performed according to the copper foil peel strength test of JIS C6481. More specifically, after heating and pressing the two-layer laminate, a cut of about 2 cm from the end is made between the two layers, and the cut end of one layer is cut with a jig of a peel strength tester. Grasping and pulling in the direction perpendicular to the aluminum plate surface, the peel strength was measured.

(5) Solder heat resistance test was performed on 85% RH After leaving it for 4 hours, it was floated in a 260 ° C. solder bath for 20 seconds. The surface of the laminate was observed and evaluated as “A” when there was no blister and “B” when there was blister.

(Production Example 1)

In hexane 395 parts of cyclohexane, 8 Echiriden one te Torashikuro ^{^{[4. 4. 0. I 2 '5}} . 1 7 1. After adding 100 parts of dodecane-3-ethylene (ETD), the temperature was raised to 60 ° C. After adding 0.3 part of 1-hexene and 4.3 parts of a 1% cyclohexane solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, the mixture was reacted for 2 hours to obtain an ETD homopolymer. Next, a hydrogenation reaction was performed using a nickel catalyst to obtain a hydrogenated ETD ring-opening copolymer.

After dissolving 100 parts of the hydrogenated product of the ring-opening copolymer and 18 parts of maleic anhydride in 233 parts of t-butylbenzene and adjusting to 13.5, 5.7 parts of dicumyl peroxyside was recycled. The reaction was carried out at 135 ° C for 6 hours while adding a solution dissolved in 47.4 parts of mouth hexanone. After completion of the reaction, 632 parts of toluene was added to the cooled reaction product solution, and the mixture was poured into isopropyl alcohol to coagulate the reaction product. The coagulated product was dried under vacuum at 100 ° C. for 8 hours to obtain a hydrogenated maleic acid-modified ring-opening polymer (Polymer A). Similarly, polymer B and polymer C were obtained in the same manner as in the production of polymer A, except that the amount of 11-hexene was changed to 1.73 parts and 4.64 parts, respectively.

Polymer A has a weight-average molecular weight (Mw) of 61700, a molecular weight distribution (Mw / Mn) of 2.7, and a maleic acid group content of 22.3 moles ⁰ /. Polymer B has a weight average molecular weight (Mw) of 25600, molecular weight distribution (MwZMn) of 1.8, maleic acid group content of 22.8 mol%, and polymer C has a weight average molecular weight (Mw) of 1 0 100, molecular weight distribution (MwZMn) is 1.5, maleic acid group content is 27.7 mol. /. Met.

Example 1 30 parts of polymer A, 40 parts of polymer B, 30 parts of polymer C, brominated bisphenol A type epoxy resin (trade name: EP IC LON 152: manufactured by Dainippon Ink Co., Ltd.) 25 parts, hydrogenated bisphenol A type epoxy Resin (trade name: EPI CLON E XA 70 15: manufactured by Dai Nippon Ink Co., Ltd.) 15 parts and 0.1 part of 1-benzyl-2-phenylimidazole 0.1 part, xylene 163 parts and cycle pentanone 1 It was dissolved in 09 parts of a mixed solvent to obtain a varnish of a thermosetting resin composition having a solid content of 34%. The viscosity of the varnish (measured at 25 ° C with an E-type viscometer; the same applies hereinafter) was 44 OmPa · S. The varnish was impregnated into the nonwoven fabric of an aramide fiber at an impregnation rate of 10 seconds, and then dried at 80 ° C for 10 minutes and at 120 at 10 minutes to obtain a solid content of the curable resin composition of 5%. 6% (solid content: base fiber content = 56:44 (weight ratio)) was obtained. The aramide fiber nonwoven fabric substrate is obtained by laminating two pieces of aramide fiber nonwoven fabric. One sheet of the prepredder was thermocompression-bonded with a vacuum press machine at 50 Kg / cm ² and a temperature of 200 ° C. for 60 minutes, and the prepredder was cured to obtain a two-layer laminate.

In addition, four of these pre-preda were superimposed and thermocompressed under the same conditions as above to obtain a four-layer laminate.

The moldability, the delamination strength, and the resistance to moisture and heat were evaluated for the two-layer laminate and the four-layer laminate obtained from the prepreg. The results are shown in Table 1.

Example 2

Example 1 was repeated except that 30 parts of polymer A, 70 parts of polymer B, and 0 parts of polymer C were used. It was dissolved in a mixed solvent to obtain a varnish of a thermosetting resin composition having a solid content of 33%. The viscosity of this varnish was 51 OmPa · S. After impregnating the varnish with the varnish fibrous nonwoven fabric substrate at an impregnation speed of 15 seconds, the varnish is dried at 80 ° C for 10 minutes and further at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition of 56%. % (Solid content: base fiber content = 56:44 (weight ratio)) I got Preda. A two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.

Example 3

The same operation as in Example 1 was carried out except that polymer A was replaced with 30 parts and polymer C was replaced with 70 parts, without using polymer B, and xylene 144 parts and cyclopentanone 95 were used. In a mixed solvent, to obtain a varnish of a thermosetting resin composition having a solid content of 37%. The varnish had a viscosity of 37 OmPa · S. After impregnating the varnish with a varnish at a rate of 10 seconds, the varnish is dried at 80 ° C for 10 minutes and further dried at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition. A pre-preda of 55% (solid content: base fiber content = 55: 45 (weight ratio)) was obtained. A two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.

Example 4

The same operation as in Example 1 was performed except that Polymer A and C were not used and Polymer B was used in 100 parts, and a mixed solvent of xylene 156 parts and cyclopentanone 104 parts was used. By dissolving, a varnish of a thermosetting resin composition having a solid content of 35% was obtained. The viscosity of this varnish was 43.5 mPa'S. The varnish is impregnated into the nonwoven fabric of the aramide fiber at an impregnation rate of 15 seconds, and then dried at 80 ° C for 10 minutes, and further dried at 120 ° C for 10 minutes to obtain a solidified curable resin composition. A pre-preda having a content of 55% (solid content: base fiber content: 55:45 (weight ratio)) was obtained. A two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.

Example 5

In Example 1, the same operation as in Example 1 was carried out except that neither Polymer A nor Polymer B was used and Polymer C was used in 100 parts, and a mixture of xylene (137 parts) and cyclopentanone (91 parts) was mixed. Dissolved in a solvent to form a thermosetting tree with a solid content of 38% A varnish of a fat composition was obtained. The viscosity of this varnish was 25 OmPa · S. After impregnating the varnish with the varnish at an impregnation speed of 5 seconds, the varnish is dried at 80 ° C for 10 minutes and further dried at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition of 57%. A pre-preda (solid content: base fiber content = 57: 43 (weight ratio)) was obtained. A two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.

Example 6

In Example 1, the same operation as in Example 1 was carried out except that the polymer A was replaced with 50 parts and the polymer C was replaced with 50 parts without using the polymer B, and xylene 196 parts and cyclopentanone 13 It was dissolved in one part of the mixed solvent to obtain a varnish of a thermosetting resin composition having a solid content of 30%. The viscosity of this varnish was 42 OmPa · S. This varnish is impregnated into the base material of the aramide fiber nonwoven at an impregnation speed of 15 seconds, and then dried at 80 ° C for 10 minutes and further at 120 ° C for 10 minutes to obtain a solid content of the curable resin composition. 57% (solid content: base material fiber amount: 57:43 (weight ratio)) was obtained. A two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1.

Comparative Example 1

The same operation as in Example 1 was carried out except that the amount of polymer A was changed to 100 parts in Example 1, and dissolved in a mixed solvent of xylene (252 parts) and cyclen pentanone (168 parts) to obtain a solid content concentration of 2 parts. 5% of a varnish of the thermosetting resin composition was obtained. The viscosity of this varnish was 39 OmPa · S. The varnish is impregnated into the base material of the aramide fiber nonwoven at an impregnation speed of 10 seconds, and then dried at 80 ° C for 10 minutes and further at 120 ° C for 10 minutes to obtain a curable resin composition. A pre-preda having a solid content of 56% (solid content: substrate fiber content = 56: 44 (weight ratio)) was obtained. A two-layer laminate and a four-layer laminate were obtained and evaluated in the same manner as in Example 1 using this pre-preda. The results are shown in Table 1. ( table 1 )

Industrial applicability

The varnish obtained by dissolving the curable resin composition of the present invention in a solvent can impregnate the base material with the curable resin composition without reducing the impregnation rate even at a high solid content.

In addition, when the pre-preda of the present invention is used, a laminate having high delamination strength and high heat resistance when absorbing moisture can be obtained.

Claims

:The scope of the claims

1. A curable resin composition containing 100 parts by weight of an alicyclic olefin polymer component and 10 to 90 parts by weight of a thermosetting component, wherein (1) the alicyclic olefin polymer At least one of the component polymers constituting the component has a polar group, and (2) at least one of the component polymers constituting the alicyclic olefin polymer component has a weight average molecular weight Mw of 5 or more. A curable resin composition characterized by being at least 0000 and less than 50,000.

2. The curable resin composition according to claim 1, wherein the polar group is a carboxyl group or a carboxylic anhydride group.

3. The curable resin composition according to claim 1, wherein the content of the polar group is 3 to 150 mol based on the total of the repeating units of all the component polymers.

4. The curable resin composition according to claim 1, wherein the content of the polar group is 6 to 150 mol based on the total of the repeating units of all the component polymers.

5. The curable resin composition according to claim 1, wherein the content of the polar group is from 10 to 80 mol based on the total of the repeating units of all the component polymers.

6. The curing method according to claim 1, wherein the ratio of the polar group in all the component polymers to the total repeating units of all the component polymers constituting the alicyclic olefin polymer is 3 to 150 mol%. Resin composition.

7. The amount of the component polymer having a weight average molecular weight Mw of not less than 500 and less than 500 is not less than 10% by weight based on the total amount of the component polymer in the alicyclic olefin polymer component. The curable resin composition according to claim 1, which is:

8. The amount of the component polymer having a weight average molecular weight Mw of 500 to 5,000 is less than 20 to 10 based on the total amount of the component polymer in the alicyclic olefin polymer component. 2. The curable resin composition according to claim 1, which is 0% by weight.

9. A component polymer having a weight average molecular weight M w of at least 500 and less than 500 2. The curable resin composition according to claim 1, wherein the amount is from 20 to 90% by weight based on the total amount of the component polymers in the alicyclic olefin polymer component.

100. The component polymer constituting the alicyclic olefin polymer component, which further contains an alicyclic olefin polymer having a weight average molecular weight Mw of not less than 500,000 and less than 900,000. The curable resin composition according to claim 1.

1 1The amount of the alicyclic olefin polymer having a weight average molecular weight Mw of not less than 500 000 and less than 900 000 is based on the total amount of the component polymers in the alicyclic olefin polymer component. 10. The curable resin composition according to claim 10, which is 90% by weight or less.

12 2. The amount of the alicyclic olefin polymer having a weight average molecular weight Mw of 5,000 or more and less than 900,000 is based on the total amount of the component polymers in the alicyclic olefin polymer component. The curable resin composition according to claim 10, wherein the content is 80% by weight or less.

13. The amount of the alicyclic olefin polymer having a weight average molecular weight Mw of 5,000 or more and less than 900,000 is based on the total amount of the component polymers in the alicyclic olefin polymer component. The curable resin composition according to claim 10, wherein the content is 10 to 80% by weight or less.

14. The curable resin composition according to claim 1, wherein the thermosetting component contains a compound containing an epoxy group.

15. A varnish containing the curable resin composition according to claim 1 and an organic solvent.

16. The varnish according to claim 15, wherein the organic solvent is a mixed solvent of a polar organic solvent and a non-polar organic solvent.

17. The varnish according to claim 15, wherein the varnish has a solid content of 5 to 70% by weight.

18. A prepreg obtained by impregnating a fiber base material with the curable resin composition according to claim 1.

19. The pre-preda according to claim 18, wherein the weight ratio of the solid content of the curable resin composition to the fiber base is from 10:90 to 90:10.

20. The prepreg according to claim 18, wherein the fiber base is made of an organic synthetic fiber.

21. A laminate having a layer obtained by curing the pre-preda according to claim 17.

Corrected form (Rule 91)