TWI289582B - Release film for printed wiring board production - Google Patents

Abstract

A release film for the production of printed wiring boards comprises a resin layer (P) comprising at least 50 wt.% polyphenylene ether resin (A). The release film has excellent releasability, is reduced in heat shrinkage, and is less apt to wrinkle printed wiring board products. The release film itself also is less apt to wrinkle. The film has excellent nonfouling properties because it suffers no bleeding. It has low hygroscopicity and excellent conformability. The film is reduced in adhesive overflowing and is excellent in adhesion between film layers and slippage between the films. It is suitable for use in producing printed wiring boards, in particular, flexible printed wiring boards.

Description

1289582 (1) Technical Field of the Invention The present invention relates to a polyphenylene ether-based resin composition, which has excellent mold release property, small heat shrinkage, difficulty in wrinkles of a printed substrate product, and a release film itself. It is also difficult to produce wrinkles, and since it does not cause precipitation, it has excellent stain resistance and is excellent in moisture absorption resistance, and is extremely suitable for use as a release film for producing a printed substrate, particularly a flexible printed substrate. [Prior Art] In the manufacturing steps of a printed wiring board, a flexible printed wiring board, and a multilayer printed wiring board, when a copper-clad laminate or a copper foil interposed between a prepreg or a heat-resistant film is thermally compressed, A release film is used; and in the manufacturing step of the flexible printed circuit board, the cover film is prevented from being thermally compressed by a thermosetting adhesive on the flexible printed circuit board forming the circuit. When a compression hot plate is adhered and a single or multi-layer printed substrate is simultaneously manufactured in plural, a method of inserting a release film for the purpose of preventing adhesion between printed substrates and protecting printed circuit boards is widely used. In recent years, the social requirements for environmental problems and safety have increased, and the heat resistance of the thermal compression molding of the release film to the printed wiring board (including PI, epoxy resin, epoxy adhesive, copper foil, etc.) The mold release function of the hot compression plate is more resistant to moisture absorption, rigidity and pollution resistance. When moisture absorption occurs, water vapor is generated during hot compression, which causes foaming: when the rigidity is lowered, Wrinkle-prone, operability is poor -4- (2) 1289582; in terms of pollution resistance, the organic or inorganic component precipitated from the release film is attached as a deposit on the surface of the printed substrate. The subsequent electroplating step cannot be carried out well, and it is necessary to have a washing step; depending on the situation, there is a big problem in product safety for products such as hard disk drives which are highly suspected of impurities. However, conventionally, a polymethylpentene film used as a release film, a ruthenium-coated polyester film, a fluorine-based film, or the like cannot sufficiently satisfy the properties required for the above-mentioned release film; that is, polymethylpentene When the film is thermally compressed and cooled, wrinkles may occur on the printed substrate due to heat shrinkage; or, in order to avoid wrinkles, it is necessary to work on the shape of the printed substrate, and the degree of freedom in shape and design is limited. Even when there is a small amount of copy on the printed substrate, the use of the printed circuit board is limited, and it cannot be said that it is sufficiently satisfied; the polyester film is coated, the heat resistance is insufficient, and the printed wiring board is damaged due to the translation of the film. The quality of the product; the fluorine-based film, although superior in heat resistance and mold release, but high in price, coupled with low rigidity, has poor handleability; although there is a proposal for cross-linking resin-type release film, rigidity and resistance The wetness is not sufficient, and it is necessary to have a problem of a complicated process of the crosslinking step; (refer to Patent Documents 1 to 4). Patent Document 1: U.S. Patent No. 4,770, 720, Patent Document 2: Patent No. 27,903,300, Patent Document 3: JP-A-2003-53, No. There is a proposal to use a film containing syndiotactic polystyrene as a release mold, but the problem of wrinkles cannot be sufficiently satisfied (see -5-1289582 (3) Patent Documents 5 to 7). Patent Document 5: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is a proposal of a release film, but it cannot be said to fully satisfy from the viewpoint of operability (rigidity) and cost (refer patent document 8). Patent Document 8: JP-A No. 200 1 - 23 3 968. Further, there is a proposal that a film made of a polyamide resin is used as a release film, but it cannot be said to be sufficiently satisfied from the release property with an adhesive. (Refer to Patent Document 9). Further, a polyether aromatic ketone resin film is proposed as a release film, but it is still a crystalline resin, and heat treatment is required to compensate for heat shrinkage. The step is not sufficiently satisfied from the viewpoint of cost (refer to Patent Document 1). In the above-mentioned prior art, a single-layer release film for a printed circuit board is produced, and practically, there is no release film containing PPE as a main component; The release film is composed of a crystalline resin, and the curing temperature of the adhesive (mainly 130 to 180 ° C is mostly in the range between the melting point and the glass transition temperature), heating and cooling in the thermal compression. In the step, it is difficult to avoid the problem of wrinkles of the release film itself and the printed substrate product due to heat shrinkage of the release film. -6 - (4) 1289582 On the other hand, in addition to the demolding function, the base film and the hot-compressed plate of the flexible printed wiring board represented by polyimine are more likely to follow-up and the overflow of the adhesive. A small amount of transparency, the adhesion between the layers of the film, the slidability of the film between the transparent coating (lacquer); follow-up, following the height difference between the yttrium imide film and the copper foil, can ease the compression of hot compression The cushioning force of the impact force; the overflow property of the adhesive is an electrode of a hole exposed by a copper foil called a flash surface in a circuit in which a base film such as polyimide or a cover film is caught In part, the extent to which the adhesive overflows due to the pressure during compression; the smaller the amount, the better; because, when the overflow is large, when the electrodes are connected by electrodes such as electrodes, connection failure occurs; It is required that the adhesion between the multilayer films is due to the problem of wrinkles in the product, even the adhesion of the surface resin and the intermediate layer resin, and it is necessary to increase the thickness of the entire film caused by laminating the third resin layer, so that the structure of the laminated film ,thin The reason why the film manufacturing step is complicated; the reason why the product is creped is presumably because the adhesion between the surface resin and the intermediate layer resin is weak, so that an air layer is generated between the layers; the slidability between the films is required because the slidability is not At a good time, the films adhere to each other and cause a decrease in operational efficiency. However, although there is a proposal to release a multilayer film having a low heat resistance resin into the intermediate layer, a release film having a higher followability can be obtained, but the level of the followability and the small amount of the adhesive overflow by the prior art described below. The interlayer adhesion between the multilayer films and the film slidability while achieving a high standard 'is not sufficiently sufficient; (refer to Patent Documents 1 1 to 16). Patent Document 11: JP-A-2000-263724, No. 1,128,582 (5) Patent Document 12: JP-A-2000- 27205 No. 5, Patent Document 13: JP-A-2003-172, Patent Document 14: JP-A-2003 - 2460 1 9 In the above prior art, a multilayer release film for a printed circuit board is actually produced, in particular, in the above prior art. A resin having a PPE-based component is not used as the outermost layer to constitute a release film; the slipperiness of the film, that is, the workability, or the small amount of the attached matter of the printed substrate product, is not sufficient. [Disclosure of the Invention] The present invention provides a composition containing a polyphenylene ether-based resin, which has excellent mold release property, small heat shrinkage, difficulty in wrinkles of a printed substrate product, and difficulty in producing a release film itself. Wrinkles; also, because it does not cause precipitation, it has excellent stain resistance and excellent moisture absorption resistance; and then, followability, a small amount of adhesion of the adhesive, adhesion between the multilayer films, and excellent slip properties between the films, It is very suitable for use as a printed substrate, especially a release film for manufacturing a flexible printed substrate. In the work of the present invention, the technique for achieving the above-mentioned problems is intensively examined. As a result of continuous investigation, it has been found that a film containing a resin composition containing a polyphenylene ether-based resin as a main component can obtain mold release property and heat shrinkage property. , wrinkle resistance, stain resistance, moisture absorption resistance, heat resistance, rigidity, and operability are excellent, and followability, a small amount of adhesion of the adhesive, and the adhesion of the multilayer film -8-(6) 1289582, The slidability between the films is excellent, and it is very suitable to use a release film for producing a flexible substrate. Thus, the present invention is at least the object of the present invention, and the printed substrate is manufactured by providing the following (1) to (16). This is achieved with a release film. (1) A release film for producing a printed circuit board comprising a resin layer (P) of 50% by weight or more of (A) a polyphenylene ether-based resin. (2) The release film for a printed circuit board according to the above (1), wherein the resin layer (P) is further contained, and the total amount of the component (A) and the component (B) is 1 〇〇 by weight. 50 parts by weight of (B) liquid crystal polyester. (3) The release film for a printed circuit board according to the above (2), wherein the resin layer (P) further contains 100% by weight of the total amount of the component (A) and the component (B) in an amount of 0.1 to 10 parts by weight. (C) A compound containing a monovalent, divalent, trivalent, or tetravalent metal element. (4) The release film for a printed circuit board according to the above (3), wherein the monovalent, divalent, trivalent or tetravalent metal element is composed of at least one of a Zn element and a Mg element. (5) The release film for a printed circuit board according to the above (2), wherein the resin layer (P) is further contained, and the total amount of the component (A) and the component (B) is 0.1 to 5 parts by weight. (D) decane compounds. (6) The release film for a printed circuit board according to the above (5), wherein the (D) decane compound is an amine group. (7) The release film for a printed circuit board according to the above (6), wherein the resin layer (P) further contains a total amount of the component (A) and the component (B)-9-9589582 (7). The (E) hydrocarbon system is in an amount of from 0. 1 to 4 parts by weight. (8) The release film for producing a printed circuit board according to the above (1), which has a single layer structure which is substantially only composed of the above resin layer (P). (9) The release film for a printed circuit board according to the above (1), which has a multilayer structure composed of the resin layer (P) and the layer (Q) containing the (F) elastomer. (10) The release film for a printed circuit board according to the above (9), wherein the (F) elastomer is a partially hydrogenated block copolymer of (G) an aromatic vinyl compound and a conjugated diene compound; Polymer. (11) The release film for a printed circuit board according to the above (10), wherein the amount of the aromatic vinyl compound in the component (G) is 5 to 65% by weight. (1) The release film for a printed circuit board according to the above (9), wherein the (F) elastomer is a copolymer of (?) ethylene and a vinyl ester compound. (1) The release film for producing a printed circuit board according to any one of the items (1) to (2), which is obtained by a squeeze tube method. (14) The release film for producing a printed circuit board according to any one of the items (1) to (1), which is obtained by a die-die extrusion method. (1) The release film for a printed circuit board according to any one of the above-mentioned items (1) to (1), wherein the contact angle between the surface of the outermost film and the water droplets is 80 degrees or more. The release film for a printed circuit board according to any one of the above-mentioned items (1) to (1), wherein the printed circuit board is a flexible printed circuit board. BEST MODE FOR CARRYING OUT THE INVENTION] The present invention is specifically described below. The (A) polyphenylene ether-based resin of the present invention is a repeating unit structure of the following (Formula 1), and is a comparative viscosity (0.5 g/d < chloroform solution, measured at 30 ° C). Is a homopolymer and/or a copolymer of 〇·15~l.Od </g; the comparative viscosity is more suitable in the range of 〇·20~0.70d </g; in the range of 0.40~0.60 The most ideal.

(wherein R, R4 are each independently a hydrogen atom, a lower alkyl group of a primary or secondary type, a phenyl group, an aminoalkyl group, a hydrocarbyloxy group; and R2 and R3 are each independently a hydrogen atom, a primary or A secondary alkyl group or a phenyl group.) Specific examples of the polyphenylene ether resin include poly(2,6-monomethyl-1,4-phenylene ether) and poly(2-methyl group). a 6-ethyl-1,4-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether) poly(2,6-dichloro- 1,4- Phenylene ether) and the like; further 'with 2 dimethyl dimethyl phenol and other phenols (for example, 2,3,6-dimethyl-11 - (9) 1289582 benzene, 2-methyl- 6 a polyphenylene ether copolymer such as a copolymer of butyl phenol; wherein poly(2,6-dimethyl-1,4-phenylene ether), 2'6-dimethylphenol and 2 The copolymer of 3,6-trimethylphenol is more suitable, and poly(2,6-dimethyl-1,4-phenylene ether) is most preferable. As an example of the method for producing (A) polyphenylene ether used in the present invention, a coordination compound of a ketone salt and an amine described in the specification of U.S. Patent No. 3 3 06 8 74 is used as a catalyst to make 2,6 - Method for oxidative polymerization of xylenol. US Patent Nos. 3 3 06875, 3 2 5 73 7 , and 3 25 73 5 8 , special public Zhao 52 — 1 7 8 8 0 and special opening 50 — 5 1 197, and special The method described in each of the publications of Kai-Zhi 63- 1 5262 No. 8 is also suitable as a method for producing (A) polyphenylene ether. The (A) polyphenylene ether resin of the present invention may be directly used as a powder after the polymerization step; or may be used as an extruder, etc., under a nitrogen atmosphere or a non-nitrogen atmosphere, to be volatile or non-volatile. Under the material, melt and knead and granulate. The (A) polyphenylene ether-based resin of the present invention also contains a polyphenylene ether functionalized with various diene novels; various diene novels such as maleic anhydride, maleic acid, Fumaric acid, phenyl maleic anhydride, itaconic acid, itaconic acid, acrylic acid, (meth)acrylic acid, methacrylic acid ester, epoxypropyl (meth) acrylate, epoxy acrylate, epoxy a compound of propyl (meth) acrylate, octadecyl acrylate, styrene or the like; and, in addition, a method of functionalizing such diene novels in the presence or absence of a radical generator , using an extruder or the like, functionalizing in a molten state under de-volatiles or non--12-1289582 (10) de-volatiles; or in the presence or absence of a free-radical generating agent, in a non-melting state, ie The temperature range above room temperature and below the melting point can be functionalized; at this time, the long-term melting point of the polyphenylene ether is, in the measurement of the differential thermal scanning calorimeter, the temperature is increased by 2 〇C / min. Inch 'observed temperature—the peak temperature of the peak of the heat flow weight chart is fixed Meaning, when the temperature of the peak is plural, the definition is based on the highest temperature. The (A) polyphenylene ether resin of the present invention is a polyphenylene ether resin alone or a mixture of a polyphenylene ether resin and an aromatic vinyl polymer, and also includes a mixture of other resins; The suspected polymer has, for example, a random polystyrene storage, a local impact polyphenylene storage, a syndiotactic polystyrene storage, a propylene, a bismuth copolymer, and the like, using polyphenylene acid and aromatic B. In the case of a polymer, the total amount of the polyphenylene ether resin and the aromatic vinyl polymer is 60% by weight or more, more preferably 7% by weight, more preferably 80%. More than weight% is most desirable. The (B) liquid crystal polyester of the present invention is a polyester which is referred to as a thermoremutation liquid crystal polymerization, and can be used as known; for example, heat of a main unit of p-hydroxybenzoic acid and polyethylene terephthalate Interconverting liquid crystal polyester, which is composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as the main unit of thermal interconverting liquid crystal polyester, with p-hydroxybenzoic acid and 4,4, dihydroxybiphenyl The thermal interconversion liquid crystal polyester or the like which is a main constituent unit of terephthalic acid is not particularly limited; the (B) liquid crystal polyester used in the present invention is used in the following structural units (a), (b) and Those who are required by (c) and/or (d) are more suitable. •13- (11) 1289582 ^(~〇~~CO-)~ ...(8)

-(~0 X 〇—^- ...(5) c—x—co^ (6) The structural units (a) and (b) are the structural units of the polyester formed by p-hydroxybenzoic acid, respectively, and the 2-hydroxyl group. a structural unit derived from 6-naphthoic acid; using the structural unit (a), (b) an excellent thermoplastic resin composition of the present invention which is excellent in balance of mechanical properties such as heat resistance, fluidity, rigidity, etc.; X) and X in (d) may be arbitrarily selected from one or more of the following (Formula 2). -14- (12) 1289582

X : -H〇)--0^〇>- [n is an integer of 1 to 6) [Y is a halogen atom, a hospital group, an aryl group]

—^〇>-CH2h^)—

(Formula 2) Suitable structures in the structural formula (C) are those formed from ethylene glycol, p-benzoquinone, 4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, and bisphenol A, respectively. Unit; more suitable are ethylene glycol, 4,4'-dihydroxybiphenyl, hydroquinone; ideal for ethylene glycol, 4,4'-dihydroxybiphenyl; structure in formula (d) Suitable for structural units of terephthalic acid, isophthalic acid and 2,6-dicarboxynaphthalene, respectively; and terephthalic acid and isophthalic acid are more preferred. _ Structural formula (c) and structural formula (d), which may be used in at least one or two or more of the above structural units; specifically, when two or more kinds are used, the structural formula (c) may be 1 Structural unit derived from ethylene glycol / structural unit derived from hydroquinone, 2 structural unit derived from ethylene glycol / structural unit derived from 4,4'-dihydroxybiphenyl, 3 derived from hydroquinone -15- 1289582 (13) Structure unit / structural unit formed by 4,4 '-dihydroxybiphenyl, etc. Further, in the structural formula (d), a structural unit derived from terephthalic acid/structural unit derived from isophthalic acid, 2 a structural unit derived from terephthalic acid, and 2,6-didecylnaphthalene The structural unit to be produced, etc.; the amount of terephthalic acid is preferably 40% by weight or more of the two components, more preferably 60% by weight or more, and particularly preferably 80% by weight or more; It is a resin composition which is 40% by weight or more of the two components and which is excellent in fluidity and heat resistance; in the liquid crystal polyester (B) component, structural units (a), (b), (c), The proportion of use of d) is not particularly limited; however, the structural units (c) and (d) are substantially equal to the molar amount. Further, the structural unit (e) formed by the structural units (c) and (d) may also be used as a structural unit in the component (B); specifically, it may be formed from ethylene glycol and terephthalic acid. The structural unit '2 is a structural unit derived from hydroquinone and terephthalic acid, 3 is a structural unit formed from 4 ' 4 ' dihydroxybiphenyl and terephthalic acid, and 4 is 4, 4' - two The structural unit of phenyl and isophthalic acid, 5 the structural unit formed by bisphenol A and terephthalic acid, and the like. -f - Ο - X - - 0 CO - X - c ο 十. (6) In the (Β) liquid crystal polyester composition of the present invention, it is not damaged in the sense of the requirements of the invention - 16 - 1289582 (14) and the characteristics of the present invention In the range of a small amount and effect, a structural unit derived from another aromatic carboxylic acid, an aromatic diol, or an aromatic hydroxycarboxylic acid can be introduced; and the component (B) of the present invention exhibits a liquid crystal state at the time of melting. The temperature (hereinafter referred to as the liquid crystal onset temperature) is preferably 1 500 to 350 ° C, more preferably 180 to 3 20 ° C; when the liquid crystal onset temperature is within this range, black impurities are obtained in the obtained resin sheet. Very few, extremely ideal. (C) A compound containing a monovalent, divalent, trivalent or tetravalent metal element, which is a metal-containing inorganic compound or an organic compound; (C) component of the present invention, which is essentially a metal element a compound constituting a component; (C) a specific example of a monovalent to tetravalent metal element, Li, Na, K, Zn, Ca, Sn, Cu, Ni, Pd, Co, Fe, Ru, Mn, Pb, Mg, Ca, Sr, Ba, A1, Ti, Ge, Sb, etc., wherein Z η, M g, T i, P b, C d, S n , S b, N i, A1, G e The elements are more suitable, and elements such as Zn, Mg, and Ti are more preferable; from the viewpoint that the (A) component and the (B) component in the resin layer (P) are not peeled off, and the toughness of the film is greatly improved, one price ~ The tetravalent metal element is most desirable for Zn and/or Mg.

(C) A specific example of a compound containing a metal element of a valence to a tetravalent value, and is preferably an oxide, a hydroxide, an alkoxide salt, an aliphatic residual acid salt, an acetate salt or the like of the above-mentioned genus element; Oxides are, ZnO, MgO, Ti〇4, Ti〇2, PbO, CdO, SnO, SbO, Sb203, NiO, Al2〇3, GeO, etc.; and, suitable hydroxides, Zn(OH) 2 , Mg(0H) 2, Ti(OH) 4, Ti(OH) 2, Pb(OH) 2, Ca(〇H) 2, Sn(OH) 2, Sb(OH) 2, SB 1289582 (15) ( OH) 3, Ni(OH) 2, Al(OH) 3, Ge(OH) 2 and the like; further, suitable alkoxy salts are Ti (isopropoxy) 4, Ti (n-butoxy) 4 and the like; in addition, suitable aliphatic carboxylates are zinc stearate, magnesium stearate, titanium stearate, lead stearate, cadmium stearate, tin stearate, barium stearate, Nickel stearate, aluminum stearate, barium stearate, etc.; particularly suitable examples thereof are ZnO, Mg(OH)2, Ti(isopropoxy)4, Ti(n-butoxy)4 , zinc acetate, zinc stearate, aluminum stearate, etc.; from the viewpoint that the layer between the (A) component and the (B) component is not peeled off, ZnO, Mg(OH) 2 is most suitable; further, these (C) components may contain impurities insofar as they do not impair the effects of the present invention. The (D) decane compound of the present invention is a functional group-containing decane compound; and is a decane compound containing at least one functional group selected from the group consisting of an amine group, a urea group, an epoxy group, an isocyanate group, and a fluorenyl group; The decane compound having a functional group may generally contain any of these functional groups in the molecule, and may be different depending on the case, and it is also preferable that the molecule contains two or more functional groups; further, the decane used in the present invention a compound, usually an alkoxydecane having a functional group as described above in the molecule; and a specific example of a functional group-containing decane compound, r-aminopropyltrimethoxydecane, r-aminopropyltriethoxy Decane, 7-aminopropylmethyldimethoxydecane, N-(cold-aminoethyl)-7-aminopropyltrimethoxydecane, N-(/3-aminoethyl)- 7 - an amino group-containing decane compound such as aminopropylmethyldimethoxydecane or 7-phenyl-r-aminopropyltrimethoxydecane; r-ureidopropyltrimethoxydecane, r Ureidopropylmethyltrimethoxydecane, r-ureidopropyltriethoxydecane, r-urea Propionyl-18- 1289582 (16) ureido-based decane compound such as triethoxy decane, r-(2-ureidoethyl)aminopropyldimethoxydecane; r-glycidoxy Propyltrimethoxydecane, r-glycidoxypropyldimethylmethoxydecane, 7-glycidoxypropyltriethoxydecane, r-glycidoxypropyl Epoxy containing ethoxylated decane, sulphide (3,4-epoxycyclohexyl)ethyltrimethoxydecane, saponin (3,4-epoxyhexyl)ethyltriethoxydecane, etc. Base decane compound; r-isocyanate propyl trimethoxy sand, 7-isocyanate propyl methyl dimethoxy decane, r-isocyanate propyl triethoxy decane, r-isocyanate propyl methyl diethoxy Isocyanate-containing decane compound such as decane, r-isocyanate propyl ethyldimethoxy decane, r-isocyanate propylethyldiethoxy decane, r-isocyanate propyl trichloromethane or the like; r-mercaptopropyl group Methyldimethoxydecane, r-sulfopropyltriethoxylate, 7-sulfopropylethyl-ethoxy-oxetane, r-mercaptopropyl Mercapto-based decane, such as methyl-diethoxy decane, decyl-decylethyltrimethoxydecane, yS-mercaptoethyltriethoxydecane, /5-mercaptoethyldimethoxydecane a compound, etc.; from the viewpoint of the toughness of the film, and from the viewpoint of not peeling off the layer between the component (A) and the component (B), it is preferable to use an amine group-containing decane compound; that is, a 7-amine Propyltrimethoxydecane, r-aminopropyltriethoxydecane, 7-aminopropylmethyldimethoxydecane, n-(/3-aminoethyl)-r-amino Propyltrimethoxydecane, n--aminoethyl)-7-aminopropylmethyldimethoxydecane is preferred. The (E) hydrocarbon wax of the present invention is substantially composed of a carbon atom and a hydrogen atom, and is actually a saturated oligomer, or a polymer, or a mixture thereof; 19- 1289582 (17) Depending on the case, The oxidizer may also have a carboxyl group or a hydroxyl group or a carbon sulfhydryl group; then, the (E) hydrocarbon wax is divided into (large) mobile paraffin and polyethylene wax; the mobile paraffin is liquid at normal temperature, and is stone. a mixture of a wax-based hydrocarbon and an alkylcycloalkane; mainly known as mineral oil; those having a specific gravity of 0.8494 or less at 15 t and containing a specific gravity of 0.8494 or more; for example, representative Coulomb Dorothy N3 5 2 (registered trademark), Iloru N542 (registered trademark), etc. are suitable for use; polyethylene wax, viscosity average molecular weight is 900~3 0000, room temperature The following are solid; the following four types can be used; that is, a monomer containing ethylene as a main component, a polymerization method at a high temperature and a high pressure by a radical polymerization catalyst, or a low pressure by a Ziegler catalyst. The method of the next polymerization, 2 will be polyethylene for general molding The solution is to obtain a low molecular weight, and 3 is obtained by separating and purifying by-product low molecular weight polyethylene in the production of general molding polyethylene, and 4 by oxidizing a general molding polyethylene ( Also known as latex wax) and the like; among them, a density of 0.92 to 0.98 (g/cm3) is suitable; and, from the viewpoint of mold release property, a viscosity average molecular weight of 900 to 1 0000 is more suitable, 1 More preferably, the amount of 000 to 4,000 is more preferable; and the type of oxidation may be used from the viewpoint of affinity with the resin composition of the present invention; in the case of the release property, 'by JIS- The acid value (KOH mg/g) obtained by the measurement of K5902 is preferably 20 or less, and more preferably 5 or less. For example, Mitsui Yila (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. is suitable for use. The resin composition of the film of the present invention is a polyphenylene ether-based resin containing 50% by weight or more; heat resistance, mold release property, heat shrinkage of the film -20-(18) 1289582 shrinkage rate, moisture absorption resistance From the viewpoint of the properties, the content is preferably 60% by weight or more, more preferably 70% by weight or more, and most preferably 80% by weight or more. In the present invention, the compounding amount of the liquid crystal polyester of the component (B) is 0.5 to 50 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and is preferably 1 to 40 parts by weight, and is preferably 2 More preferably, it is preferably 30 parts by weight, and from the viewpoints of mold release property and fluidity, from the viewpoint of the anisotropy of the liquid crystal polymer and the thickness difference of the film, the upper limit of the compounding amount is preferably 50 parts by weight; The lower limit of the blending amount is preferably 5% by weight, and further, from the viewpoints of mold release property and rigidity (operational property relating to film processing) of the polyimide film of the base film of the flexible printed circuit board. In other words, (B) the liquid crystal polyester is more suitable in the above-mentioned amount. In the present invention, the compounding amount of the component (C) is 100 parts by weight of the total of (A) and (B) from the viewpoint of layer peeling of the component (A) and the component (B) in the film, and specific gravity and heat resistance. It is preferred to contain 〇·ΐ~1 〇 by weight, more preferably 〇 2 to 5 parts by weight, and particularly preferably 0.4 to 3 parts by weight; the content of the component (C) is less than 〇·i by weight. When the film itself is peeled off, the specific gravity is increased, and when it exceeds 10 parts by weight, the specific gravity is increased and the heat resistance is lowered. In the present invention, the blending amount of the component (D) is from the viewpoint of peeling and stable production of the layer (A) component and the component (B) in the film, and the total weight of (A) and (B) is 1 〇〇. The portion is preferably contained in an amount of o. id, more preferably 0.15 to 3 parts by weight, particularly preferably 0.2 parts by weight; and when the content of the component (D) is less than 0.1 part by weight, the film itself The layer 21 - (19) 1289582 is more remarkably peeled, and when it exceeds 5 parts by weight, an unsuitable side reaction such as decomposition, crosslinking, or the like may occur, and the composition of the present invention may not be obtained stably. In the present invention, the blending amount of the '(E) hydrocarbon wax is from the viewpoint of mold release property and precipitation, and the total amount of the components (A) and (B) is 100 parts by weight, and the weight is 〇1 to 4 Preferably, it is preferably 0.3 to 3 parts by weight, more preferably 0.5 to 2 parts by weight; and the amount of the component (E) is less than 0.1 part by weight, and a sufficient release from the adhesive cannot be obtained. When the amount is more than 4 parts by weight, the component (E) is precipitated on the printed substrate after thermal compression. In the present invention, in addition to the above-mentioned components, additional components such as an antioxidant, a flame retardant, an elastomer [ethylene/propylene copolymer, ethylene) may be added as needed insofar as the characteristics and effects of the present invention are not impaired. /1 - Butene copolymer, ethylene/propylene/nonconjugated diene copolymer, ethylene/ethyl acrylate copolymer, ethylene/ethylene methacrylate copolymer, ethylene/vinyl acetate/( Methyl)acrylic acid propylene propyl ester copolymer and ethylene/propylene-g-maleic anhydride copolymer, olefin-based copolymer such as ABS, polyester polyether elastomer, polyester polyester elastomer, and vinyl aromatic Compound-conjugated diene compound block copolymer, hydride of ethylene-based aromatic compound-co-diene compound block copolymer], plasticizer (epoxidized soybean oil, polyethylene glycol, fatty acid ester, etc.) ), flame retardant additives, weathering (light) improvers, various colorants, and the like. The release film for printing a printed circuit board of the present invention contains a film of a thermoplastic resin layer (P) having the above resin composition; therefore, the release film for a printed circuit board of the present invention can be printed on a wiring board. In the manufacturing steps of a flexible printed wiring board, a multilayer printed wiring board, etc., -22- 1289582 (20) is used for protecting a prepreg or a heat-resistant film interposed therebetween, and thermally compressing a copper-clad laminate or a copper foil. The printed substrate can be used to prevent contamination of the adhesive due to the thermal compressor or cushioning material. The release film for a printed circuit board having a multilayer structure according to the second aspect of the present invention will be described below. The resin layer (D) of the present invention and the layer (Q) containing the (F) elastomer have a multilayer structure. A release film for a printed circuit board is obtained by using the above-mentioned resin layer (P) as an outermost layer and sandwiching a layer containing (F) an elastomer layer (Q); basically (p) / (Q) / (P) three-layer structure, depending on the situation, an adhesive layer can be inserted between the (P) layer and the (Q) layer to form a five-layer structure; however, from the viewpoint of film thickness and simplicity, The three-layer structure is most suitable. The elastomer of the component (F) of the present invention is a partially hydrogenated block copolymer of an aromatic vinyl compound-conjugated diene compound block copolymer and (G) an aromatic vinyl compound and a conjugated diene compound. Polymer, (H) copolymer of ethylene and vinyl ester compound, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/propylene/non-conjugated diene copolymer, ethylene/propylene-g-horse An anhydride copolymer, an olefin copolymer such as ABS, a polyester polyether elastomer, a polyester polyester elastomer, etc.; in a copolymer of (Η) ethylene and a vinyl ester compound, a vinyl ester compound means For vinyl monomers containing an ester group or a carboxyl group; for example, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, acrylic acid, ( Methyl)acrylic acid and the like; especially in the (F) component, from the viewpoint of the adhesion between the followability and the multilayer film, the (G) aromatic vinyl compound and the conjugated diene -23- 1289582 ( 21) part of the block copolymer of the compound a hydrogenated polymer, and a copolymer of (Η) ethylene and a vinyl ester compound; and a partially hydrogenated polymer of a block copolymer of the (G) aromatic vinyl compound and the conjugated diene compound; First, a block copolymer of an aromatic ethylenic compound and a conjugated dimeric compound is a polymer block segment mainly composed of an aromatic vinyl compound and a polymer mainly composed of a conjugated diene compound. a block copolymer formed by a block segment; a specific example of the aromatic vinyl compound, at least one selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and Vinylbenzene, p-methylstyrene, 1,1-diphenylstyrene, etc., wherein styrene is most suitable; and specific examples of the conjugated diene compound are at least one selected from the group consisting of butadiene and isoprene Iso, 1,3 - pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3 — Butadiene, etc., which is best suited to the combination of Ding Yi, Yi Wu, and the combination of this temple. (G) component of the polymer 'from the viewpoint of heat resistance, heat resistance and lower generation characteristics, preferably partial hydrogenation; and its hydrogenation rate is preferably 5 to 100%; and further, from the viewpoint of thermal stability In other words, the hydrogenation rate is more preferably 50% or more; the structural characteristics of the partially hydrogenated block copolymer are in accordance with the features of JP-A-6-34049, which is to satisfy the special opening 61. In the case of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations of the stipulations, the TUF τ EX (registered trademark), Kuleidong Kuradong (registered trademark) manufactured by Polymer Japan Co., Ltd., Danalong manufactured by JSR Co., Ltd., Xiepudong (registered trademark) manufactured by Kuraray Co., Ltd., and Haibralu (registered trademark 289582 ( 22) Mark) and so on. In particular, as a property of a release film, the binding amount of the aromatic vinyl compound in the component (G) is 5 to 5 from the viewpoints of heat resistance, followability, and adhesion between the (P) layer and the (Q) layer. 65 wt% is more suitable, more preferably 10 to 60 wt%, and particularly preferably 30 to 50 wt%; when the amount is less than 5 S wt%, it is difficult to express sufficient heat resistance, and heat for producing a neem substrate is _ In the case of shrinkage, there is a case where the layer (P) overflows, adheres to a compressor, a buffer material, or the like; and when it exceeds 65 wt%, it is difficult to exhibit sufficient followability and sufficient interlayers of (P) and (Q) Confidence. The resin layer CP) containing 50% by weight or more of the (A) polyphenylene ether-based resin is excellent in handleability in a single-layer film having extremely high rigidity, but it has a small amount of adhesion to the stomach and a small amount of adhesion of the adhesive. A film having a multilayer structure is more suitable for use in the production of a printed circuit board in which the adhesion between the multilayer films and the slidability between the films is used. The thickness of the release film of the present invention is 3 to ΙΟΟμηη when a single-layer film is used, and more preferably 10 to ΙΟΟμηι from the viewpoint of cost and handling property, and 30 to 60 μm is most preferable; when a multilayer film is used; , the total thickness is 50~3 00 μιη, from the viewpoint of followability and operability, 70~2 50 μm is preferred, and 100~200 μιη is more suitable; for multilayer structure, for total thickness, middle layer The ratio of the thickness of (Q) is preferably 50% or more, more preferably 60% or more, more preferably 70% or more; and when the ratio is less than 50%, followability cannot be sufficiently exhibited. The resin composition of the present invention can be produced by various methods; for example, a uniaxial extruder, a boring extruder, a roller machine, a kneader, a Brabender plastic-25- 1289582 (23) change machine, Banbury A method of melt-kneading or the like of a kneader or the like, wherein a method of melt-kneading using a twin-screw extruder is most preferable; at this time, the melting_mixing temperature is not particularly limited, and usually may be 1 to 5 0~ Any choice of 3 5 0 °c - choose. _ The release film for producing a printed circuit board of the present invention can be obtained by extruding a film using the obtained resin composition as a raw material; and the raw material component of the resin composition of the present invention can be directly added to the extruded film. The molding machine is obtained by blending and film forming at the same time. φ The release film for producing a printed circuit board of the present invention can be produced by using a squeeze tube method, which is also called a blow molding method depending on the case, and the Parson which leaves the cylinder is not cooled immediately, and is appropriately selected 50~ 29 (The temperature in the TC range, controlling the temperature of the Parson, can make the thickness of the sheet uniform, and it is extremely important in the production of the sheet of the resin composition which is not peeled off; the resin of the (P) layer can be used, and Q) The resin of the layer is a multi-layer laminated film having a multi-layer structure. On the other hand, the release film for producing a printed circuit board of the present invention can be produced by a T-die extrusion molding method; It can be used without stretching, and it can be used for uniaxial stretching or biaxial stretching. It is expected that when the strength and rigidity of the film are high, stretching has its effect; the resin of (P) layer is derived from resin, and (Q) The method for laminating a resin component by a layer is a dry lamination method, a co-extrusion lamination method, or the like; in the case of dry lamination, in a (P) layer, a single layer film, a T-die Feeding the single layer film near the top, while the (Q) layer is The resin (F) elastomer is extruded from a T-die and can be laminated by a roller; this method is particularly suitable for the resin viscosity of the (P) layer and the -26-1289582 (24) (Q) layer being greatly different; On the one hand, in the case of co-extrusion lamination, a multi-layer molding die is used, and the resin component of the (P) layer and the resin component of the (Q) layer can be laminated by an extruder; The release film for a printed circuit board of the present invention has a contact angle of the outermost film surface with ice droplets of 80° or more; from the viewpoints of mold release property and moisture absorption resistance, It is preferably 80 degrees or more, preferably 85 degrees or more, more preferably 90 degrees or more; when the enthalpy is less than 80 degrees, the mold release property may not be sufficiently exhibited, and the moisture absorption resistance may not be sufficiently exhibited; the thin surface and The contact angle of the water droplets can be measured at room temperature (23 ° C), for example, using a solid-liquid interface analysis device, Drop Master (trademark) manufactured by Kyowa Interface Science Co., Ltd. a printed substrate in a release film comprising epoxy A rigid printed circuit board represented by a fat, and a flexible printed circuit board represented by a polyimide, and more recently, an exhaust gas such as a flexible printed circuit board, a mobile phone, or a hard disk drive (HDD). The specification of the contamination is very strict, and it is very suitable for use in a flexible printed circuit board from the viewpoint of excellent stain resistance of the release film of the present invention. Thus, the release film for a printed circuit board of the present invention is obtained. Excellent moldability, small heat shrinkage, difficulty in wrinkles of printed substrate products, and the release film itself is difficult to produce wrinkles; and, because no precipitation occurs, the stain resistance is excellent, and the hygroscopicity is more, and then it follows. The adhesiveness of the adhesive, the adhesion of the adhesive, the adhesion between the multilayer films, and the slidability between the films are extremely suitable for the production of a printed substrate, in particular, a release film of a flexible printed -27-(25) 1289582 substrate. [Embodiment] [Embodiment] The present invention is described by way of Examples, and the present invention is not limited thereto without departing from the gist of the present invention. [Production Example 1] Production Example of Polyphenylene Ether (PPE-1) 2'6-Dimethylphenol was oxidatively polymerized to obtain a powdery poly(2,6-dimethyl group) having a comparative viscosity of 0.42. 1,4-phenylene ether). [Production Example 2] Production Example of Liquid Crystalline Polyester (LCP-1) Under a nitrogen atmosphere, by adding a hydrazinic acid, a 2-pyridyl-6-carotic acid, an acetic anhydride, and heating and melting to carry out polycondensation, The liquid crystal polyester (LCP-1) of the following theoretical formula; further, the composition of the composition is expressed in terms of molar ratio.

k/丨=〇·73/〇·27 -28- (26) 1289582 2—Hydroxy—6 [Production Example 3] Production example of liquid crystal polyester (LCP-2) Under a nitrogen atmosphere, p-hydroxybenzoic acid was added. - naphthoic acid, p-benzoquinone, isophthalonitrile, acetic anhydride, heat-melting and polycondensation', which has the following theoretical slaughter type liquid polyacetate (LCp-2). The composition is expressed in terms of molar ratio.

0· 〇·Η〇^·

•CO

CO

k/|/m/n = 0.7/0.2/0.1/0.1

The film formation and physical property evaluation of each resin composition was carried out in the following manner. (1) Blow molding to obtain the obtained pellets by a tube extruder at a temperature of 290 ° C, a cylindrical die extrusion die temperature of 290 C, and a screw shaft diameter of 50 mm. Extrusion sheet molding; the air pressure of blowing is set to a thickness of up to 5 to 111 degrees. In the case of a multilayer film, the air pressure of the blowing is adjusted to be adhered by the pinch roll melting -29- 1289582 (27), and the thickness is (p) layer (Q) layer (p) layer 3 Ο μ m of three layers Film structure. (2) The T-die is extruded to form the uniaxial extruder with the venting holes of the granules at a cylinder temperature of 300 ° C, a T-die temperature of 300 ° C, and a screw shaft diameter of 65 mm. The discharge amount is 60 kg/hr, the thickness of the T-die gap is 0.15 mm, the width of the die gap is 6 5 〇mm, the surface temperature of the calender roll is 130 ° C, and the pull-out speed is controlled to make the thickness up to 50 μπι. Extrusion film molding. When preparing a film of a multi-layer structure, a three-layer type extruder is used, a three-layer die head of a feeding block type, a total discharge amount of 60 kg/hr, a width of a die slit of 65 0 mm, and a calender roll surface temperature of 130 are used. °C, control the pull-out speed' so that the thin fl旲 thickness can reach the (P) layer 30μπι, (Q) layer 150μιη, (Ρ) layer 30μιη three-layer film structure, and extrusion film forming. (3) The film thickness is cut into a width of 500 mm and a length of 200 mm; a total of 1 point in the upper and lower sides of the five points in the width direction is measured, and the same measurement is performed on the other piece to determine the total of 20 points. Hey, find the average 値. (4) The contact angle is fixed on the stage by using the solid-liquid interface analysis device Drop Master 5〇〇 (registered trademark) manufactured by Kyowa Interface Science Co., Ltd., on the film. One drop of distilled water (2 μί ) was dropped to measure the contact angle, and the average enthalpy was determined by measuring the enthalpy point; it was carried out at room temperature (23 ° C). (5) Mold release -30- 1289582 (28) A polyimide film having a thickness of 25 μm (Popong 100 Η (registered trademark) manufactured by DuPont Co., Ltd.) was used as a base film, and an epoxy resin having a thickness of 2 μm was used. The adhesive is interposed between them, and a copper box with a thickness of 35 μm and a width of 50 μm is adhered to obtain a copper-clad laminate (i); secondly, a polyimide film having a thickness of 25 μm [Capriton 1 Ο 制 manufactured by DuPont) Η (registered trademark)], coated with a 20 μm thick epoxy-based adhesive having a flow start temperature of 80 ° C to obtain a cover film (ii); and a thickness of 50 μm obtained by the above (1) and (2) The film is used as a release film (iii); (ii) the epoxy-based adhesive layer is connected to the copper foil of (i), and the film is overlapped in the order of (i), (ii), (iii), at 190 After 1 minute of hot compression at °C and 50kgf/cm2, a flexible printed substrate is obtained; after the thermal compression, the release film (iii) and the polyimide film (i) and (Π) are pulled apart. Then, the mold release property was judged based on the following criteria. The release property from the surface of the substrate is "release property against FPC"; the release property of the adhesive and copper foil exposed by the overflow surface (electrode hole) of (i) and (ii) is "pair" Adhesive", copper foil release." 〇: No resistance, no peeling. △: When peeling off, there is a slight resistance X: It is completely adhered and is not easily peeled off. After peeling (in the case of X, strong peeling), it was confirmed whether or not the release film was broken. (6) Heat shrinkage ratio The release film obtained in the above (1) and (2) was flattened on MD and TD, and cut into 150 mm X 150 mm in an oven set at 1 90 °C. The heat was fixed for 5 minutes, and taken out and allowed to cool. Measurement -31 - 1289582 (29) The dimensions of the MD and TD before and after heating were determined, and the heat shrinkage rate was determined according to the following formula. Heat shrinkage rate (%) = (side length before heating - length of side after heating) / (length of side before heating) X 1〇〇MD is extruded by a blow molding machine or by a T-die The direction of resin flow of the molding die of the molding machine, TD is the direction perpendicular to the MD. (7) Wrinkles of FPC (Flexible Printed Substrate) are carried out in addition to the above (3, except for the use of a polyimine film having a thickness of 12.5 μm X 150 mm X 250 mm [Capital 50H (registered trademark)] manufactured by DuPont Co., Ltd. In the same compression test, the obtained FPC was taken out to confirm the presence or absence of wrinkles of the FPC. (8) Precipitating 1 A polyimide film having a thickness of 125 μm (available from DuPont, Kapudong 500H (registered trademark)) is smashed at 190° with the release film obtained in the above (1) or (2). C, 30kgf / cm2, for 5 minutes of hot compression; then, after peeling off the release film, on the surface of the polyimide film in contact with the release film, water-based singular ink (the thickness of the nib is about 1 · 5 mm ) After scribing for 5 minutes, the discharge state of the water-based singular ink was visually observed, and the precipitation property was determined according to the following criteria. 〇: The state of the water-repellent singular ink is not discharged. X = The state of the water-repellent singular ink (9) Precipitating 2 - 32 - 1289582 (30) Polyimide film at a thickness of 125 nm [made by DuPont, Capo 5 0 0H (registered trademark)], an epoxy adhesive having a thickness of 20 μm was applied by a rod, and cured at 50 ° C for 2 hours to prepare an adhesive-coated polyimide film; On the coated surface, the release film obtained in the above (1) or (2) was superposed and thermally compressed at 19 (TC, 30 kgf/cm 2 for 5 minutes; thereafter, the release film was peeled off, as described above (4) The method of measuring the contact angle of the surface of the adhesive coated surface of the polyimide. On the other hand, the blank test is performed by applying pressure at 190 ° C without applying pressure on the above-mentioned adhesive-coated polyimide film. After a minute, it was cooled, and the contact angle on the surface was measured to be 58 degrees; therefore, compared with the contact angle of the blank test (58 degrees), the difference was large, and it was judged that a substance was precipitated on the polyimine side. Moisture absorption resistance The film obtained in the above (1) or (2) is cut into a rectangular shape having a size of 100 X 1 9 Onm. , using a constant temperature and humidity tank (Taibayes Co., Ltd., ?1^3??), under 85, 95% relative humidity in a humidified environment, after exposure for 48 hours, Calculate the weight increase rate (Δ W) and calculate the average enthalpy of each of the two films; the smaller the weight increase rate (Aw), the better the moisture absorption resistance. Weight increase rate (Aw) (%) = (wi — w〇) /w〇x 100 [where w! is the weight of the film after warming and humidification (g); w〇 is dried in a hot air dryer at 100 °C for 2 hours before heating and humidification, In the dryer, put the film weight (g) after cooling to room temperature «33- 1289582 (31). (11) Heat resistance The obtained pellets are used at a cylinder temperature of 320/330/320/3 1 0 °C. Injection molding machine (IS-80EPN 'Toshiba Machinery Co., Ltd.) having a firing rate of 85% and a mold temperature of 90 ° C was injection-molded; however, the cylinder temperatures of Comparative Example 1 and Comparative Example 2 were both set at 280. (: proceeding; forming into ASTM Donzacu test piece with a thickness of 3.2 mm x 127 mm x 12.7 mm; using the obtained molded piece, measured according to ASTM-D648, under a load of 1.82 MPa (12) Rigidity The same test piece as (1 1 ) above is used for the automatic curve charting machine (made by Shimadzu Corporation, AG - 5000), according to the ASTM-D790 standard, at 23 ° The flexural modulus and flexural strength were measured under the atmosphere of C. [Example 1] φ Polyphenylene ether (PPE-1) and liquid crystal polyester (LCP-1) and zinc oxide (Ζηο, Dongbang Zinc Co., Ltd.) Company system, Yinling-1) According to the ratio (parts by weight) shown in Table 1, the barrel temperature of only the top material side is 250 °C, and the cylinder temperature and die temperature are set to 310 °C. A double-shaft extruder (made by WERNER & PFLEIDERER, ZSK-, 25) with a venting port is melt-kneaded to obtain a granule; the granule is T-shaped as shown in the above (2) The die is extruded to obtain a film having an average thickness of 51 nm; the film is evaluated according to the above method; the results are shown in Table 1; • 34-1289582 (32) The deflection temperature of the load is 184 ° C, and the flexibility is changed. The rate is 2670 MPa. [Example 2] Except that polystyrene (GP, PS Japan Co., Ltd., G 9 3 0 5 ) was used as the component (A), and each component was blended in the ratio (parts by weight) shown in Table 1, The same procedure as in Example 1 was carried out to obtain particles; the T-die shown in the above (2) was extrusion-molded to obtain a film having an average thickness of 5 μm; the film was evaluated by the above method, and the result was as follows. As shown in Table 1, the load deflection temperature was 167 ° C, and the flexural modulus was 2740 MPa. [Example 3] Except that LCP-2 was used as the component (B), liquid paraffin (wax!, manufactured by Yakusson Mobiru Co., Ltd., Cullysdorj N - 3 5 2, a colorless liquid at normal temperature) As the component (E), each component is blended in the same ratio (parts by weight) as shown in Table 1 except that it is the same as in Example 2, that is, the pellet is obtained; the T-die of the above (2) is not obtained. The pressure molding was carried out to obtain a film having an average thickness of 49 μm; the film was evaluated by the above method, and the results are shown in Table 1; the deflection temperature of the load was 168 t, and the bending elastic modulus was 275 MPa. [Example 4] In addition to using high-impact polystyrene (HIPS, manufactured by PS Japan Co., Ltd., H9405) as the component (A), polyethylene wax [wax 2, manufactured by Mitsui Chemicals Co., Ltd.] (registered trademark), 405MP, white solid at room temperature] In place of wax 1, each component is in the same ratio as shown in Table-1 -35 - 1289582 (33) (please divide). The obtained pellets were extrusion-molded using the τ-type die shown in the above (2) to obtain a film having an average thickness of 50 μm; the film was evaluated by the above method, and the results are shown in Table 1; the deflection temperature of the load was 16 3 °C, bending elastic modulus is 2820MPa °

-36- 1289582

A 撇 辑 2 H 1 '"< 〇〇〇· OO m csi τ*Ή Ο 〇〇壊〇\ csi 〇CNl CD 壊X 1 0.021 Comparative Example 3 Csl un oo 沄v〇卜.〇X wn Ο o 壊〇1 0.041 Comparative Example 2 O i—H o <] X OO CO r" H 〇1 〇1 ίΤ) C5 Comparative Example 1 ot—H t—H un g ί "Η 〇〇壊-0.95 OO m 〇X 0.019 Example 9 δ ON OO 〇〇壊s 〇so 壊〇1 0.016 Example 8 〇i-HOS 〇〇壊o 00 mo 壊〇1 0.043 Example 7 wn ON CN c<ioom oo 〇〇壊rH 〇go 壊〇1 0.032 Example 6 VO VO 寸 C<ls oo 〇〇壊soso 壊〇1 0.046 Example 5 o ο csi 04 ν/Ί t—i <1 ·ι 〇〇壊2 O o壊〇0.021 Example 4 5S \〇v〇〇〇· r—HO in 〇〇壊o csi CS o 〇S 0.024 Example 3 oo σ\ oo o wn On S 〇〇壊oo 壊〇0.019 Example 2 m oo cn inch oo Oo 〇〇 o o o o o 〇 1 0.018 Example 1 ir^ ON vn oo 〇〇壊o ... csi 〇〇0.024 ώ Oh PU Ο HIPS LCP-l LCP-2 o Mg(OH)2 decane 1 ... ...< m CNJ m SEBSl SEBS2 Change PPE X9102 s CU s Film thickness 〇im) Contact angle (°c) Ph _ Film glass P 2 QH FPC wrinkle precipitation 1 1 Precipitation 2 (°) Hygroscopicity Aw (%) 褂承 N_^ £ ^3" w Other ig -37- 1289582 (35) [Example 5] In addition to using magnesium hydroxide (manufactured by Wako Pure Chemical Co., Ltd., special grade) instead of zinc oxide, as (C The components and other components are also blended in the proportions shown in Table 1, and the other ones are obtained in the same manner as in Example 3, that is, the particles are obtained; and the T-die shown in the above (2) is extruded to obtain an average thickness. 5 2 um film; film evaluation was carried out according to the above method, and the results are shown in Table 1; the load deflection temperature was 158 tons; and the bending modulus was 2600 MPa. [Example 6] A partially hydrogenated polymer using a block copolymer of an aromatic vinyl compound and a conjugated diene compound [SEBS1, manufactured by Asahi Kasei Chemicals Co., Ltd., Taft Vehicle H1272 (registered trademark); SEBS2, manufactured by Asahi Kasei Chemicals Co., Ltd., Taftku H1 041 (registered trademark)], as other components other than (A) to (E), and other components are also blended in the proportions shown in Table 1. Others were the same as in Example 5, that is, the particles were obtained; and the film having the average thickness of 60 μm was obtained by the blow molding shown in the above (1); the film was evaluated by the above method, and the results are shown in the table. 1 shows; the load deflection temperature is 150 ° C; the bending elastic modulus is 23 00 MPa ° .

[Example 7] Except for the use of an amine group-containing decane compound [decane 1, N-(yS-aminoethyl)-r-aminopropyl-38- 1289582 (36) manufactured by Shin-Etsu Chemical Co., Ltd. Dimethoxy decane, trade name KBM — 602], the substitution component (C) is used as the component (D), and the other components are also blended in the ratios shown in Table 1, and the others are the same as in the embodiment 6, that is, A pellet obtained by the above (1), that is, a film having an average thickness of 40 μm; the film was evaluated by the above method, and the results are shown in Table 1; the deflection temperature of the load was 176 t: bending elasticity The rate is 2740 MPa. [Example 8] φ High heat-resistant modified PPE resin using a blend of polyphenylene ether and polystyrene resin [Modified PPE, manufactured by Asahi Kasei Chemicals Co., Ltd., Zhayilong X9102 (registered trademark) As a resin composition containing PPE, according to the blow molding shown in the above (1), a film having an average thickness of 4 um is obtained; the film is evaluated by the above method, and the results are shown in Table 1; The flexural temperature was 159 ° C and the flexural modulus was 23 60 MPa. [Example 9] φ In addition to the component (A), the other components were blended in the same ratio as shown in Table 1, and the same procedure as in Example 1 was carried out to obtain pellets; the blow molding shown in the above (1) , that is, a film having an average thickness; the film was evaluated according to the above method. The results are shown in Table 1; the load deflection - temperature was 143 ° C, and the bending modulus was 2100 MPa °. [Comparative Example Π Poly 4 Methyl-1-pentene-based resin [manufactured by Mitsui Chemicals Co., Ltd. -39- 1289582 (37), PMP, RT18, TPX (registered trademark)] as pellets, blow molding as shown in (1), ie A film having an average thickness of 51 μm was obtained; the film was evaluated by the above method, and the results are shown in Table 1; the deflection temperature of the load was 10 ° C, and the bending modulus was 1 28 0 MPa. [Comparative Example 2] Polyethylene terephthalate resin (PET, NEH205 0, manufactured by Unica Card Co., Ltd.) was used as a pellet, and was extruded by a τ-type die shown in (2). That is, an average thickness of 50 μm was obtained; the evaluation of the film was carried out by the above method, and the results are shown in Table 1; the deflection temperature of the load was 75 ° C, and the flexural modulus was 2420 MPa. [Comparative Example 3] The pellets were obtained in the same manner as in Example 1 except that the components (A) to (C) were blended in the ratio shown in Table 1, and the T-die shown in the above (2) was obtained. Extrusion, that is, a film having an average thickness of 50 μm; the film was evaluated by the above method, and the results are shown in Table 1; the deflection temperature of the load was 172 ° C, and the flexural modulus was 5100 MPa. [Example 1] Except that the components (A), (B), (C), and (E) were blended in the ratios shown in Table 1, the same procedures as in Example 1 were carried out to obtain granules; 2) The T-die shown is extruded to obtain a film with an average thickness of 5 2 μm; the film is evaluated according to the above method, and the result is -40-9589582 (38) as shown in Table 1; The bending temperature is 151 ° C. The bending elastic modulus is 24 MPa. From the above, the film of the resin layer (P) containing 50% by weight or more of the polyphenylene ether resin of the present invention has a good mold release property. The heat shrinkage is small, it is difficult to cause wrinkles on the printed substrate product, and the release film itself is hard to wrinkle, and since no precipitation occurs, the stain resistance is excellent, and the moisture absorption resistance is excellent, and it is extremely suitable for use in manufacturing a flexible printed circuit board. Release film. Next, the release film for producing a printed circuit board having a multilayer structure according to the second aspect of the invention will be described below. (13) Follow-up film is placed on a brass plate with a deep 3〇um groove, and pressed at 180°C, 3kg/cm2, 3 minutes using thermal compression to visually observe the trap. In the case of the groove, the followability is judged by the following criteria. 〇: The replication of the groove is extremely good. X: The groove is not reproducible, or wrinkles are generated around the groove. (14) Overflow of the adhesive When the above-mentioned (5) release property evaluation is performed, the amount of the overflow surface (electrode hole) having a diameter of 1.5 mm is overflowed by the adhesive after the compression, and is observed by an optical microscope. The benchmark is used to assess the spillage of the adhesive. 〇: The amount of the adhesive overflow is less than 0.08 mm △: When the amount of the adhesive overflow is 0.08 to 0.15 mm X: The amount of the adhesive overflow is 0.1 5 nm or more (15) P - The adhesion between the Q layers - 41 - (39) 1289582 〇: The film of the P layer and the Q layer is not peeled off. X: The film of the P layer and the Q layer is easily peeled off or not completely adhered. (16) Slidability: The two layers of the multilayer film are overlapped, and the film is pressed at room temperature, 5 kg/cm2, and 15 seconds, and only the film of the upper layer is slid, and the lower layer is judged according to the following criteria. Slidability of the film; performed 3 times. 〇: It will not stick to the lower film three times, and the upper film can slide separately. X: At least one time is stuck to the underlying film, and the upper film cannot be slid separately. [Production Example 4] Production Example (P-i) of Resin Layer (P) The pellet obtained in Example 1 was used as it was. [Production Example 5] Production Example (P-ii) of Resin Layer (P) The pellet obtained in Example 2 was used as it was. [Manufacturing Example 6] Production examples (P-iii), (Pi v ), and (P-v) of the resin layer (P) were carried out in the same manner as in Example 1 except that the ratios shown in Table 2 were blended. That is, the particles are obtained. [Manufacturing Example 7] Production Example of Resin Layer (P) (P - vU using Zhayilong X9 1 02 by Asahi Kasei Chemicals Co., Ltd. (Note 1288582 (40) Trademark)' is used as Example 8 High heat-resistant modified ppE resin. Table 2 Pi P-ii P-iii P-iv Pv P-vi (A) PPE-1 95 83 95 83 65 GP 13 13 20 Group (B) LCP-1 5 4 5 4 15% (C)ZnO 0.8 0.8 0.8 0.8 (D) decane-1 0.2 (E) La-1-1 La-2-2 Modified PPEX 9 1 0 2 100

[Production Example 8] Production Example (P-vii) of Resin Layer (P): Maleic Anhydride (Special Grade, manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts by weight φ, (PPE-1) 80 parts by weight, high impact polymerization Styrene (manufactured by Ps Japan Co., Ltd., H9405) 15 parts by weight, and polystyrene (made by ps Japan Co., Ltd., 685), 5 parts by weight, and the same as in Production Example 4, which was functionalized with maleic anhydride. Polyphenylene ether-based resin composition. [Production Example 9] Production example of partially hydrogenated polymer (SEBS - i ) of block copolymer of aromatic vinyl compound and conjugated diene compound. Synthesis of polybutadiene-polyphenylene having polystyrene hydrogenation Ethylene structure, -43- 1289582 (41) The combined styrene content is 35 %, the number average molecular weight is 6, 2, Ο Ο, molecular weight distribution is 1.05, and the 1,2-vinyl bond of polybutadiene before hydrogenation is 38. %, the partial hydrogenated polymer of the block copolymer having a hydrogenation ratio of the polybutadiene portion of 99.9%. [Production Example 1] Production Example of Partially Hydrogenated Polymer (s EBS - ii ) of Block Copolymer of Aromatic Vinyl Compound and Conjugated Diene Compound Synthesis of Polybutadiene Polymerized by Polystyrene Hydrogenation The styrene structure, the amount of bound styrene is 60%, the number average molecular weight is 89,000, the molecular weight distribution is 1.0, and the 1,2-vinyl binding amount of the polybutadiene before hydrogenation is 38%, and the polybutadiene portion is A partially hydrogenated polymer of a block copolymer having a hydrogenation rate of 99.8%. [Production Example 11] A method of producing a partially hydrogenated polymer (s EBS - iii ) of a block copolymer of an aromatic vinyl compound and a conjugated diene compound is disclosed in JP-A-63-9925 Using 1,3 dimethyl- 2-imidazolidinone; that is, having a polystyrene-hydrogenated polybutadiene-polystyrene structure, a combined styrene amount of 8%, a number average molecular weight of 51,000, and a molecular weight distribution I.04, a polybutadiene having a 1,2-vinyl grouping amount of 38% of a block copolymer having an amine group at the terminal; and a hydrogenation ratio of a polybutadiene portion obtained by hydrogenation and synthesis is 99.8 Partially hydrogenated polymer of % block copolymer. [Production Example 1 2] Production of a partially hydrogenated polymer (SEBS-1V) of an aromatic vinyl compound and a conjugated diene compound of 1,298,582 (42) block copolymer having a polystyrene-hydrogenated polybutene The polystyrene structure, the bound styrene amount 3%, the number average molecular weight 52,000, the molecular weight distribution 1.05, the 1,2-vinyl bond content of the polybutadiene before hydrogenation is 38%, and the polybutadiene storage portion A partially hydrogenated polymer of a block copolymer having a hydrogenation rate of 99.9%. [Production 13] A production example of a partially hydrogenated polymer (SEBS-v) of an aromatic vinyl compound and a conjugated diene compound embedded in a φ segment copolymer having a polystyrene-hydride-hydrogenated polybutylene-polyphenylene The structure of B is 70%, the number of styrene is 85%, the number average molecular weight is 82,000, the molecular weight distribution is 1.05, the 1,2-vinyl bond of polybutadiene before hydrogenation is 38%, and the hydrogenation rate of polybutadiene is 9 9.9. Part of the hydrogenated polymer of the block copolymer. [Example 11] Using (P-i) as a (P) layer 'partial hydrogenated polymer (S EB S i) using a block copolymer of an aromatic vinyl compound and a conjugated diene compound For the (Q) layer, the film was evaluated by the above-described method using the τ-type die extrusion molding method shown in (2) above, that is, a multi-layer film, and the results are as shown in Table 3. Show. [Example 12] A multi-layer film of the same manner as in Example 1 except that (P - i ) was replaced by (P - ii ) as the (p) layer; the above method was carried out. • 45- 1289582 (43) Evaluation of the film, the results of which are shown in Table 3. [Example 13] Except that (P-1) was replaced by (P - U1) as a layer, by the blow molding extrusion method of the above (1), a multi-layer film was produced, and the same as in Example 1 1 The same evaluation of the film was carried out, and the results are shown in Table 3. [Example 14] A multi-layer film which was the same as that of Example 11 except that (P - i ) was replaced by (P - iv ) as the layer (p); the evaluation of the film was carried out by the above method. The results are shown in Table 3. [Example 15] A multi-layer film was produced in the same manner as in Example 11 except that (P - i ) was replaced by (P - v ) as the (P) layer; the evaluation of the thin film was carried out according to the above method. The results are shown in Table 3. [Example 16] Except that (SEBS — i ) was replaced by (SEBS — Π ) as a part of the (Q ) layer/block copolymer of the aromatic vinyl compound and the conjugated diene compound. A multi-layer film was prepared in the same manner as in Example 1; the film was evaluated by the above method, and the results are shown in Table 3. -46 - (44) 1289582 [Embodiment 17] Except that (P - i ) is replaced by (P - vi ) as (P) layer, (SEBS - i) is replaced by (SEBS - ii) as (Q) layer A multi-layer film prepared in the same manner as in Example 11 except for the partial hydrogenated polymer of the block copolymer of the aromatic vinyl compound and the conjugated diene compound; the film was evaluated by the above method, and the result was as follows. as shown in Table 3. [Example 18] Except that (P-1) was replaced by (P-vii) as the (P) layer, (SEBS-i) was replaced by (SEBS-m) as the (Q) layer of the aromatic vinyl compound and A multilayer film of the same composition as that of Example 11 except for the partial hydrogenated polymer of the block copolymer of the conjugated diene compound was used; the evaluation of the film was carried out by the above method, and the results are shown in Table 3. [Example 19] The ethylene-vinyl acetate copolymer [EVA-1, manufactured by Asahi Kasei Chemicals Co., Ltd., Sant Ku EF0925 (registered trademark), VA content 9 wt%, MFR = 2.5 g/10 min) was replaced ( SEBS — i) As the (Q) layer, the single layer film obtained by the T-die method of the above (2) is fed to the upper and lower sides of the T-die, and the EVA-1 resin is melted. The state flows out of the dicing die to dry lamination of the first roller set at 165 ° C, that is, a film of a multi-layer structure; the thickness of the P/Q/P layer is 30/1 50/30 μm. (45) 1289582 [Example 20] A film of a multi-layer structure which was produced by a dry lamination method in the same manner as in Example 19 except that (P-1) was replaced by (P-iv) as the (p) layer. The thickness of the P/Q/P layer is 25/1 50/25 urn. [Example 21] Except that (SEBS - i ) was replaced by (SEBS - iv ) as the (Q) layer, the others were all carried out in the same manner as in Example 1; the interlaminar adhesion of p-q was X' . [Example 22] Except that (SEBS - Π was replaced by (SEBS - v) as the (Q) layer, the same operation as in Example 11 was carried out; the followability was χ, and the overflow property of the adhesive was Δ. Example 4] In addition to the use of poly-4-methyl-1-pentene resin [PMP, RT18, ΤΡΧ (registered trademark), manufactured by Sanwa Chemical Co., Ltd.] as the (Ρ) layer, the implementation is as shown in (1) In addition to the blow molding, the same multilayer film as in Example 1 was used; the evaluation of the film was carried out according to the above method, and the results are shown in Table 3. Ρ - The adhesion between the Q layers was poor, and it was not possible to estimate [Comparative Example 5] -48- (46) 1289582 In addition to polyethylene terephthalate (PET, NEH2050, manufactured by Unica Card Co., Ltd.) as the (P) layer The other multilayer film was prepared in the same manner as in Example 11; the evaluation of the film was carried out by the above method, and the results are shown in Table 3; the adhesion between the P-Q layers was poor, and the followability and slidability could not be evaluated.

• 49- 1289582 (47) Example 6 Ph S 1 T-type die r—Η 〇〇X <] 1 X Comparative Example 5 Oh SEBS-i P/Q/PT type die VsD 卜<X 1 〇 X 1 Comparative Example 4 Oh s SEBS-i P/Q/P blow molding f1 H 〇〇1 〇X 1 Κ Κ > pL EVA-i P/Q/P τ-type die σ\ oo 〇〇〇〇〇 〇孽 2 2 鹣ώ EVA-i P/Q/P Τ-type die on oo 〇〇〇〇〇〇 base Oh SEBS-iii P/Q/P Τ-type die ί ί * PU SEBS-ii P/Q/P Τ-type die CS| oo 〇〇〇〇〇〇Example 16 £ SEBS-ii P/Q/P Τ-type die to oo 〇〇〇〇〇〇孽 2 2 &gt ; cu SEBS-i P/Q/P Τ 丨 〇〇〇〇〇〇 四 (4) geisha > z SEBS-i P/Q/P Τ 模 〇 oo 〇〇〇〇〇〇 2 U :l SEBS-i P/Q/P Blow molding oo 〇〇〇〇〇〇Example 12 Oh SEBS-i P/Q/P Τ-type die oo 〇〇〇〇〇〇 二 2* CU SEBS- i P/Q/P Τ type 1 die oo 〇〇〇〇〇〇 o o layer forming method c for FPC adhesion agent, copper I foil follow-up adhesive overflow PQ interlayer Closeness, slidability, ts, ts, detachment, temperament

-50- 1289582 (48) [Comparative Example 6] Poly(4-methyl-1-pentene-based resin [PMP, RT18, TPX (registered trademark), manufactured by Mitsui Chemicals, Inc.] was used as the (P) layer. A single layer release film having no (Q) layer; the evaluation of the film was carried out in the same manner as above, and the results are shown in Table 3. According to the present invention, the film of the multilayer structure comprising the (P) layer of the (A) polyphenylene ether resin and the (Q) layer containing the (F) elastomer is excellent in mold release property. The followability, the adhesion of the adhesive, the adhesion between the multilayer films, and the slidability between the films are excellent, and are extremely suitable for use in the production of printed substrates, particularly in the manufacture of flexible printed substrates. [Industrial Applicability] According to the present invention, it is possible to provide a polyphenylene ether-based resin composition, which has excellent mold release property, small heat shrinkage, difficulty in wrinkles of a printed circuit board product, and difficulty in wrinkles in the release film itself; Moreover, since the appearance of the precipitate does not occur, the stain resistance is excellent, and the moisture absorption resistance is excellent. Then, the followability, the overflow property of the adhesive, the adhesion between the multilayer films, and the slidability between the films are excellent, and are extremely suitable. A release film for producing a printed substrate, in particular, a flexible printed substrate is used. The present invention has been described in detail above, and various changes and modifications can be made without departing from the spirit and scope of the invention. The present application is based on a Japanese patent application filed on Apr. 18, 2003 (Japanese Patent Application No. 2003- 1 1 3843), and Japanese Patent Application No. 2003-119849, filed on Apr. 23, 2003. And extract its contents as a reference. -51 -

Claims (1)

1289582 ————— I Year ί月分分9修 (more} 正本拾, patent application scope 93 1 1 0773 Patent application Chinese application patent scope amendments. Amendment of September 27, 1995. 1. A manufacturing printing A release film for a substrate, characterized in that the resin layer (P) contains (A) a polyphenylene ether resin of 50% by weight or more, and (B) a liquid crystal polyester, and (B) a component (A) and (B) The total weight of the component is 100 parts by weight, and is 0.5 to 50 parts by weight. 2 · The release film for producing a printed circuit board according to the first aspect of the patent application' wherein the resin layer (P) is further contained, A) The total weight of the component and the component (B) is 100 parts by weight, and is 0.1 to 10 parts by weight of (C) a compound containing a monovalent, divalent, trivalent or tetravalent metal element. The release film for producing a printed circuit board according to Item 2, wherein the monovalent, divalent, trivalent or tetravalent metal element is formed by at least one of a Zn element and a Mg element. A release film for producing a printed circuit board, wherein the resin layer (P) is further contained, and the (A) component is B) The total weight of the component is 100 parts by weight, and is 0.1 to 5 parts by weight of the (D) decane compound. 5 . The release film for producing a printed circuit board according to claim 4, wherein the (D) decane compound has 6. A release film for producing a printed circuit board according to the fifth aspect of the invention, wherein the resin layer (P) further contains 100 parts by weight of the total weight of the component (A) and the component (B), and is 0.1. ～4 parts by weight of the (E) hydrocarbon system. 1289582 7. The release film for producing a printed circuit board according to the first aspect of the invention, which has a single layer structure consisting essentially only of the above resin layer (P) 8. The release film for producing a printed circuit board according to the first aspect of the invention, which has a multilayer structure comprising the resin layer (P) and the layer (Q) containing the (F) elastomer. A release film for producing a printed circuit board according to claim 8 wherein (F) an elastic system, (G) a partially hydrogenated polymer of a block copolymer of an aromatic vinyl compound and a conjugated diene compound I 〇 · Manufacturing printing as claimed in item 9 of the patent application The release film for a substrate, wherein the amount of the aromatic vinyl compound in the component (G) is 5 to 65 wt%. II. The release film for printing a printed circuit board according to the scope of claim 8 ' F) an elastic system (Η) a copolymer of ethylene and a vinyl ester compound. The release film for a printed circuit board according to any one of claims 1 to 11, which is formed by a squeeze tube method. The release film for a printed circuit board according to any one of claims 1 to 11, which is obtained by a die-die extrusion method. The release film for producing a printing substrate according to any one of the preceding claims, wherein the surface of the outermost film is at a contact angle with water droplets of 80 or more. The release film for a printed substrate according to any one of claims 1 to 11, wherein the printed substrate is a flexible printed substrate.