JP3909852B2 - Release film for printed circuit board manufacturing - Google Patents

Description

  The present invention relates to a release film used in manufacturing a printed circuit board, particularly a flexible printed circuit board. More specifically, the present invention relates to a release film having a polyphenylene ether-based resin composition, excellent in releasability, stain resistance, and moisture absorption resistance, hardly causing wrinkles on a printed circuit board product, and hardly causing wrinkles on the release film itself. .

  In a manufacturing process of a printed wiring board, a flexible printed wiring board, a multilayer printed wiring board, etc., a release film is used when a copper-clad laminate or a copper foil is hot-pressed through a prepreg or a heat-resistant film. In addition, in the manufacturing process of a flexible printed circuit board, when the cover lay film is hot-press bonded with a thermosetting adhesive to the flexible printed circuit board body on which the electric circuit is formed, the cover lay film and the press hot plate are bonded. Method of inserting a release film for the purpose of preventing adhesion of printed circuit boards or protecting printed circuit board products when simultaneously manufacturing a plurality of single or multilayer printed circuit boards Is widely practiced.

Conventionally, as a release film, a polymethylpentene film, a silicone-coated polyester film, a fluorine-based film, a syndiotactic polystyrene film, an alicyclic polyolefin film, a polyamide film, and a polyether aromatic ketone resin film have been proposed. . (For example, Patent Documents 1 to 4)
However, the proposed release film cannot be said to be sufficient in terms of releasability from a coverlay film or the like, wrinkles due to heat shrinkage or heat resistance.
Furthermore, in recent years, due to increasing environmental demands and social demands for safety, these release films have heat resistance that can withstand hot press molding, printed wiring boards (PI, epoxy resin, epoxy adhesive, copper foil, etc.) In addition to functions such as mold release from a hot press plate, moisture absorption resistance, rigidity, and contamination resistance have been demanded.

Japanese Patent Publication No. 6-2369 Japanese Patent No. 2790330 JP 11-349703 A JP-A-6-316032

  The object of the present invention is to provide a release film that is excellent in releasability, stain resistance, and moisture absorption resistance and has a small thermal shrinkage (that is, it is difficult to wrinkle printed circuit board products and the release film itself does not wrinkle). Is to provide.

As a result of intensive studies on the technology for achieving the above-mentioned problems, the present inventors have found that a film having a resin composition mainly composed of a polyphenylene ether resin is excellent in the above characteristics and suitable as a release film used in the production of a printed circuit board. As a result, the present invention has been completed.
That is, the present invention
1. (A) A release film for producing a printed circuit board comprising a resin layer (P) containing 50 to 99.5 parts by weight of a polyphenylene ether resin and (B) 0.5 to 50 parts by weight of a liquid crystal polyester,
2. A resin containing 0.1 to 10 parts by weight of a compound containing (C) an I-valent, II-valent, III-valent or IV-valent metal element with respect to a total of 100 parts by weight of the component (A) and the component (B) 2. A release film for producing a printed circuit board according to 1 above, comprising a layer (P),
3. (C) The release film for producing a printed circuit board according to 2 above, wherein the I-valent, II-valent, III-valent, or IV-valent metal element is a resin layer (P) in which the element is Zn and / or Mg.
4). (A) The total amount of 100 parts by weight of the component and the (B) component, wherein (D) the resin layer (P) containing 0.1 to 5 parts by weight of the silane compound is used. Release film for printed circuit board production,
5. (D) The release film for producing a printed circuit board according to 4 above, wherein the silane compound comprises a resin layer (P) which is a silane compound having an amino group,
6). Any one of the above 1 to 5 comprising the resin layer (P) containing 0.1 to 4 parts by weight of a hydrocarbon wax (E) with respect to 100 parts by weight of the total of the component (A) and the component (B) Release film for manufacturing printed circuit board according to the description,
7). A release film for producing a printed circuit board having a single layer structure, comprising the resin layer (P) according to any one of 1 to 6 above,
8). A release film for producing a printed circuit board having a multilayer structure comprising the resin layer (P) according to any one of 1 to 6 above and (F) a layer (Q) containing an elastomer,
9. (F) The release film for producing a printed circuit board according to 8 above, wherein the elastomer is a partially hydrogenated polymer of a block copolymer of (F1) an aromatic vinyl compound and a conjugated diene compound,
10. (F1) The release film for producing a printed circuit board according to 9 above, wherein the component is a partially hydrogenated polymer of a block copolymer having an aromatic vinyl compound bond amount of 5 wt% to 65 wt%,
11. (F) The release film for producing a printed circuit board according to 8 above, wherein the elastomer is a copolymer of (F2) ethylene and a vinyl ester compound,
12 A release film for producing a printed circuit board according to any one of the above 1 to 11 , obtained by molding by an extruded tubular method,
13. A release film for producing a printed circuit board according to any one of 1 to 11, obtained by molding by a T-die extrusion method,
14 14. The release film for producing a printed circuit board according to any one of 1 to 13 above, wherein the contact angle between the film surface of the outermost surface layer and water droplets is 80 ° or more, and The release film for producing a printed circuit board according to any one of the above 1 to 14, wherein the printed circuit board is a flexible printed circuit board.

  According to the present invention, it has become possible to provide a release film that is excellent in releasability, stain resistance, and moisture absorption resistance and that has low thermal shrinkage.

Hereinafter, the present invention will be specifically described.
The (A) polyphenylene ether resin of the present invention has a repeating unit structure of (Formula 1), and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.15 to 1.0 dl / A homopolymer and / or copolymer in the range of g. A more preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.

(R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₂ and R ₃ each independently represent hydrogen Represents primary or secondary lower alkyl or phenyl)

  Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2 -Methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, Polyphenylene ether copolymers such as 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

(A) As an example of the production method of polyphenylene ether, there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. The methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, Japanese Patent Publication Nos. 52-17880, and JP-A-50-51197 and 63-152628 are also available ( A) It is preferable as a method for producing polyphenylene ether.
(A) The polyphenylene ether-based resin may be used as a powder after the polymerization process, or using an extruder or the like, under a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, under devolatilization or under non-devolatilization You may use it by pelletizing by melt-kneading.

  The (A) polyphenylene ether resin also includes polyphenylene ether functionalized with various dienophile compounds. Examples of various dienophile compounds include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl allylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene, and the like. Can be mentioned. Furthermore, as a method of functionalizing with these dienophile compounds, the functionalization may be performed in a molten state under devolatilization or non-devolatilization using an extruder or the like in the presence or absence of a radical generator. Alternatively, the functionalization may be performed in a non-molten state, that is, in a temperature range from room temperature to the melting point in the presence or absence of a radical generator. At this time, the melting point of the polyphenylene ether is defined by the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min in the differential thermal scanning calorimeter (DSC) measurement. If there are a plurality of peak top temperatures, it is defined as the highest temperature among them.

  (A) The polyphenylene ether resin includes a polyphenylene ether resin alone or a mixture of a polyphenylene ether resin and an aromatic vinyl polymer, and further includes a mixture of other resins. Examples of the aromatic vinyl polymer include atactic polystyrene, high impact polystyrene, syndiotactic polystyrene, acrylonitrile-styrene copolymer, and the like. When a mixture of a polyphenylene ether resin and an aromatic vinyl polymer is used, the polyphenylene ether resin is 60 wt% or more, preferably 70 wt% or more, based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer. More preferably, it is 80 wt% or more.

  The (B) liquid crystal polyester of the present invention is a polyester called a thermotropic liquid crystal polymer, and known ones can be used. For example, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and polyethylene terephthalate, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, p-hydroxybenzoic acid Examples thereof include thermotropic liquid crystal polyesters mainly composed of acid, 4,4'-dihydroxybiphenyl and terephthalic acid, and are not particularly limited. (B) As liquid crystalline polyester, what consists of following structural unit (a), (b), and (c) and / or (d) as needed is used preferably.

Here, the structural units (A) and (B) are respectively a structural unit of a polyester generated from p-hydroxybenzoic acid and a structural unit generated from 2-hydroxy-6-naphthoic acid. By using the structural units (a) and (b), it is possible to obtain the thermoplastic resin composition of the present invention having an excellent balance of mechanical properties such as excellent heat resistance, fluidity and rigidity. X in the structural units (c) and (d) can be arbitrarily selected from the following (Formula 2), respectively.

In the structural formula (c), preferred are structural units formed from ethylene glycol, hydroquinone, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, and bisphenol A, and more preferred are ethylene glycol, 4 4,4'-dihydroxybiphenyl and hydroquinone, and particularly preferred are ethylene glycol and 4,4'-dihydroxybiphenyl. In the structural formula (d), preferred are structural units formed from terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene, and more preferred are terephthalic acid and isophthalic acid.
In the structural formula (c) and the structural formula (d), at least one or two or more of the structural units listed above can be used in combination. Specifically, when two or more kinds are used in combination, in the structural formula (c), 1) a structural unit generated from ethylene glycol / a structural unit generated from hydroquinone, 2) a structural unit generated from ethylene glycol / 4,4 Examples include structural units formed from '-dihydroxybiphenyl, 3) structural units formed from hydroquinone / 4, structural units formed from 4,4'-dihydroxybiphenyl, and the like.

  In the structural formula (d), 1) a structural unit generated from terephthalic acid / a structural unit generated from isophthalic acid, 2) a structural unit generated from terephthalic acid / 2, a structural unit generated from 2,6-dicarboxynaphthalene , Etc. Here, the amount of terephthalic acid is preferably 40 wt% or more, more preferably 60 wt% or more, and particularly preferably 80 wt% or more in the two components. By setting the amount of terephthalic acid to 40 wt% or more of the two components, a resin composition having relatively good fluidity and heat resistance can be obtained. The proportion of the structural units (A), (B), (C), and (D) in the liquid crystal polyester (B) component is not particularly limited. However, the structural units (c) and (d) are basically in equimolar amounts.

  Moreover, the structural unit (e) consisting of the structural units (c) and (d) can also be used as the structural unit in the component (B). Specifically, 1) a structural unit produced from ethylene glycol and terephthalic acid, 2) a structural unit produced from hydroquinone and terephthalic acid, 3) a structural unit produced from 4,4'-dihydroxybiphenyl and terephthalic acid, 4) And structural units formed from 4,4'-dihydroxybiphenyl and isophthalic acid, and 5) structural units formed from bisphenol A and terephthalic acid.

  (B) The liquid crystalline polyester component is a structural unit formed from another aromatic dicarboxylic acid, aromatic diol, or aromatic hydroxycarboxylic acid within a small range that does not impair the features and effects of the present invention as necessary. Can be introduced. The temperature at which the liquid crystal state at the time of melting of the component (B) (hereinafter referred to as liquid crystal start temperature) is preferably 150 to 350 ° C, more preferably 180 to 320 ° C. Setting the liquid crystal start temperature within this range is preferable because less black foreign matter is present in the resulting resin sheet.

  The (C) compound containing an I-valent, II-valent, III-valent or IV-valent metal element of the present invention is an inorganic compound or organic compound containing a metal. The component (C) is a compound essentially containing a metal element as a main constituent component. Specific examples of metal elements that can take I, II, III, or IV in the component (C) include Li, Na, K, Zn, Cd, Sn, Cu, Ni, Pd, Co, Fe, Ru, Examples include Mn, Pb, Mg, Ca, Sr, Ba, Al, Ti, Ge, and Sb. Of these, Zn, Mg, Ti, Pb, Cd, Sn, Sb, Ni, Al, and Ge elements are preferable, and Zn, Mg, and Ti elements are more preferable. From the standpoint that the (A) component and the (B) component in the resin layer (P) are not separated and the toughness of the film is greatly improved, the metal element of I, II, III, or IV is Zn and Or it is especially preferable that it is Mg element.

(C) As specific examples of the compound containing a metal element of I, II, III, or IV, oxides, hydroxides, alkoxide salts, aliphatic carboxylates, and acetates of the above metal elements are desirable. . Furthermore, examples of preferable oxides include ZnO, MgO, TiO ₄ , TiO ₂ , PbO, CdO, SnO, SbO, Sb ₂ O ₃ , NiO, Al ₂ O ₃ , and GeO. Examples of preferred hydroxides include Zn (OH) ₂ , Mg (OH) ₂ , Ti (OH) ₄ , Ti (OH) ₂ , Pb (OH) ₂ , Cd (OH) ₂ , Sn (OH ) ₂ , Sb (OH) ₂ , Sb (OH) ₃ , Ni (OH) ₂ , Al (OH) ₃ , Ge (OH) _{2 and the} like. Examples of preferred alkoxide salts include Ti (O ⁱ Pr) ₄ and Ti (O ⁿ Bu) ₄ . Examples of preferred aliphatic carboxylates include zinc stearate, magnesium stearate, titanium stearate, lead stearate, cadmium stearate, tin stearate, antimony stearate, nickel stearate, aluminum stearate, stearic acid. Examples include germanium. Among these, particularly preferred specific examples include ZnO, Mg (OH) ₂ , Ti (O ⁱ Pr) ₄ , Ti (O ⁿ Bu) ₄ , zinc acetate, zinc stearate, and aluminum stearate. Furthermore, ZnO and Mg (OH) ₂ are preferable from the viewpoint of no delamination between the component (A) and the component (B). Moreover, these (C) components may contain the impurity in the range which does not impair the effect of this invention.

  The (D) silane compound of the present invention is a functional group-containing silane compound and contains at least one functional group selected from the group consisting of an amino group, a ureido group, an epoxy group, an isocyanate group, and a mercapto group. Silane compound. The functional group-containing silane compound usually only needs to contain any one of these functional groups in the molecule, but in some cases, two or more of these functional groups are contained in the molecule. It may be what you do. Moreover, the silane compound used in the present invention is usually an alkoxysilane containing a functional group as described above in the molecule. Specific examples of the functional group-containing silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy. Silane compounds containing amino groups such as silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ Silane compounds containing a ureido group such as ureidopropylmethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropylmethyltriethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane; Glycidoxypropyl Methoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β -Silane compounds containing an epoxy group such as (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanate Isocyanes such as propylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane A silane compound containing a radical group; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptoethyltrimethoxysilane, silane compounds containing mercapto groups such as β-mercaptoethyltriethoxysilane and β-mercaptoethyldimethoxysilane;

Furthermore, the silane compound which has an amino group from a viewpoint of the toughness of a film and the viewpoint of the absence of delamination between (A) component and (B) component is preferable. That is, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) ) -Γ-aminopropylmethyldimethoxysilane.
The (E) hydrocarbon wax of the present invention is substantially composed of carbon and hydrogen, and is substantially a saturated oligomer or polymer or a mixture thereof. Depending on the case, it may be oxidized and may have a carboxyl group, a hydroxyl group, or a carbonyl group. And (E) hydrocarbon wax is roughly divided into liquid paraffin and polyethylene wax. Here, the liquid paraffin is a liquid at room temperature, and is mainly a mixture of paraffin hydrocarbons and alkylnaphthene hydrocarbons. Sometimes called mineral oil. A specific gravity at 15 ° C. of 0.8494 or less and a specific gravity at 15 ° C. exceeding 0.8494 are included. For example, as a typical example, Cristol N352 (registered trademark), Prime Mall N542 (registered trademark) manufactured by ExxonMobil Co., Ltd. can be suitably used.

Here, the polyethylene wax has a viscosity average molecular weight of 900 to 30,000, and the following four types that are solid at room temperature can be used. That is, 1) those obtained by polymerizing monomers mainly composed of ethylene at high temperature and high pressure with a radical polymerization catalyst, or by polymerizing at low pressure with a Ziegler catalyst. What can be obtained by the method of molecular weight 3) What can be obtained by separating and purifying by-product low molecular weight polyethylene when producing polyethylene for general molding 4) What can be obtained by the method for oxidizing polyethylene for general molding (Sometimes called an emulsion wax). Among them, those having a density of 0.92 to 0.98 (g / cm ³ ) are preferable. From the viewpoint of releasability, those having a viscosity average molecular weight of 900 to 10,000 are preferred, and those having 1,000 to 4,000 are more preferred. An oxidized type can also be used from the viewpoint of affinity with the resin composition of the present invention. In that case, from the viewpoint of releasability, the acid value (KOH mg / g) obtained by the measurement of JIS K5902 is preferably 20 or less, more preferably 5 or less. For example, as a typical example, Mitsui High Wax (registered trademark) manufactured by Mitsui Chemicals, Inc. is preferably used.

The resin composition of the film in this invention contains (A) polyphenylene ether-type resin 50weight% or more. From the viewpoint of heat resistance, releasability, heat shrinkage, and moisture absorption resistance of the film, the content is preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
The blending amount of the (B) liquid crystal polyester in the present invention is 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the total of the component (A) and the component (B). Preferably it is 2-30 weight part. From the viewpoint of anisotropy of the liquid crystal polymer and uneven thickness of the film, the blending amount is preferably 50 parts by weight or less. From the viewpoint of releasability and fluidity, the amount is preferably 0.5 parts by weight or more. Moreover, it is preferable that (B) liquid crystalline polyester exists in the said compounding quantity from a viewpoint of mold release property and rigidity (workability regarding film handling) with the polyimide film which is a base film of a flexible printed circuit board.

The blending amount of the component (C) in the present invention is based on 100 parts by weight of the total of (A) and (B) from the viewpoint of delamination, specific gravity and heat resistance of the component (A) and component (B) in the film. The content is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and particularly preferably 0.4 to 3 parts by weight.
The blending amount of the component (D) in the present invention is based on 100 parts by weight of the total of (A) and (B) from the viewpoint of delamination and stable production of the component (A) and the component (B) in the film. The content is preferably 0.1 to 5 parts by weight, more preferably 0.15 to 3 parts by weight, and particularly preferably 0.2 to 1 part by weight.

The blending amount of the (E) hydrocarbon wax in the present invention is 0.1 to 4 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B) from the viewpoint of releasability and bleeding out. Is preferably 0.3 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight.
In the present invention, in addition to the above-described components, other additional components as necessary, for example, an antioxidant, a flame retardant, an elastomer (ethylene / propylene copolymer, Ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and Ethylene / propylene-g-maleic anhydride copolymer, olefin copolymer such as ABS, polyester polyether elastomer, polyester polyester elastomer, vinyl aromatic compound-conjugated diene compound block copolymer, vinyl aromatic compound-conjugated Hydrogenated diene compound block copolymer), plastic (Epoxidized soybean oil, polyethylene glycol, fatty acid esters), flame retardant agents, weathering (light) resistance improvers, may be added various colorants, and the like.

The release film for producing a printed circuit board of the present invention may be a film having a single layer structure composed of the resin layer (P) having the above resin composition, or from the resin layer (P) and other resin layers. A film having a multilayer structure may be used.
In particular, in a release film used in the production of a flexible printed circuit board, a cushioning property (hereinafter abbreviated as “following property”) that closely adheres to a step between a polyimide film and a copper foil and relaxes an impact force during pressurization of a hot press. ), A film having a multilayer structure is more preferable.
The release film for producing a printed circuit board having a multilayer structure is preferably a release film for producing a printed circuit board having a multilayer structure comprising a resin layer (P) and a layer (Q) containing an elastomer (F). In particular, a structure in which the resin layer (P) is the outermost layer and the layer (Q) containing the elastomer (F) in the middle is sandwiched is preferable. A three-layer structure of (P) / (Q) / (P), or a five-layer structure can be formed by inserting an additional adhesive layer between the (P) layer and the (Q) layer. However, a three-layer structure is preferable from the viewpoints of film thickness and simplification.

As the elastomer of component (F), aromatic vinyl compound-conjugated diene compound block copolymer, partially hydrogenated polymer of block copolymer of aromatic vinyl compound and conjugated diene compound, copolymer of ethylene and vinyl ester compound Olefin copolymers such as ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / propylene-g-maleic anhydride copolymer, ABS, A polyester polyether elastomer, a polyester polyester elastomer, etc. are mentioned.
In particular, in the component (F), from the viewpoint of followability and adhesion between multilayer films, (F1) a partially hydrogenated polymer of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and (F2) ethylene and a vinyl ester compound These copolymers are preferred.

  (F1) A partially hydrogenated polymer of a block copolymer of an aromatic vinyl compound and a conjugated diene compound will be described below. First, here, a block copolymer of an aromatic vinyl compound and a conjugated diene compound is a block copolymer comprising a polymer block segment mainly composed of an aromatic vinyl compound and a polymer block segment mainly composed of a conjugated diene compound. It is a polymer. Specific examples of the aromatic vinyl compound include at least selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, divinylbenzene, p-methylstyrene, 1,1-diphenylstyrene, and the like. One or more types can be selected, and styrene is particularly preferable. Specific examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3. -At least 1 sort (s) chosen from butadiene etc. can be selected, and a butadiene, isoprene, and these combination are especially preferable.

  Here, the polymer of the component (F1) is preferably partially hydrogenated from the viewpoint of heat resistance and heat deterioration characteristics. Further, the hydrogenation rate is preferably 5 to 100%. Further, from the viewpoint of thermal stability, those having a hydrogenation rate of 50% or more are more preferable. As the structural characteristics of the partially hydrogenated block copolymer, one or more kinds can be used in combination as long as the requirements described in detail in JP-A-61-34049 are satisfied. Typical examples include TUFTEC (registered trademark) manufactured by Asahi Kasei Chemicals Corporation, KRATON (registered trademark) manufactured by Kraton Polymer Japan Co., Ltd., DYNARON manufactured by JSR Corporation, and SEPTON manufactured by Kuraray Co., Ltd. (Registered trademark) and HYBRAR (registered trademark).

In particular, as a release film characteristic, from the viewpoint of heat resistance, followability, and adhesion between the (P) layer and the (Q) layer, the aromatic vinyl compound bond amount in the component (F1) is 5 wt% to 65 wt%. It is preferably 10% to 60% by weight, more preferably 30% to 50% by weight.
(F2) In the copolymer of ethylene and a vinyl ester compound, the vinyl ester compound refers to a vinyl monomer containing an ester group or a carboxyl group. Examples thereof include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid, methacrylic acid and the like.

The thickness of the release film of the present invention is 3 to 100 μm when used as a single layer film. From the viewpoint of cost and handleability, 10 to 100 μm is more preferable, and 30 to 60 μm is particularly preferable. When used in a multilayer film, the total thickness is 50 to 300 μm, preferably 70 to 250 μm, and more preferably 100 to 200 μm from the viewpoint of followability and workability. In the case of a multilayer structure, the ratio of the thickness of the intermediate layer (Q) to the total thickness is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more.
The resin composition of the present invention can be produced by various methods. For example, a heat melt kneading method using a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer or the like can be mentioned. Among them, a melt kneading method using a twin screw extruder is most preferable. Although the melt kneading temperature in this case is not particularly limited, it can usually be arbitrarily selected from 150 to 350 ° C.

The release film for manufacturing a printed circuit board of the present invention can be obtained by extrusion film molding using the resin composition obtained above as a raw material, or the raw material components derived from the resin composition of the present invention are directly fed into an extrusion film molding machine. However, blending and film forming can be carried out simultaneously.
The release film for producing a printed circuit board of the present invention can be produced by an extrusion tubular method, and in some cases a method called an inflation method. In order to prevent the parison coming out of the cylinder from cooling immediately, the temperature of the parison is appropriately selected from the temperature range of 50 to 290 ° C., and controlling the temperature of the parison makes the sheet thickness uniform. It is extremely important in preparing a sheet without delamination of each component. A film having a multilayer structure can be obtained by multilayer lamination of the resin derived from the (P) layer and the resin component derived from the (Q) layer.

  On the other hand, the release film for producing a printed circuit board of the present invention can be produced by T-die extrusion. In this case, it may be used without stretching, may be uniaxially stretched, or may be obtained by biaxially stretching. Stretching is effective for increasing the strength and rigidity of the sheet. Examples of the method of multi-layer lamination of the resin derived from the (P) layer and the resin component derived from the (Q) layer include dry lamination and coextrusion lamination. In the case of dry lamination, a single layer film of (P) layer is manufactured once, and this single layer film is fed from the top and bottom in the vicinity of the T die, while (F) elastomer, which is a resin derived from (Q) layer, is used. It can be extruded from a T-die and laminated with a roll. This method is particularly effective when the viscosities of the (P) layer and (Q) layer resins are greatly different. On the other hand, in the case of coextrusion lamination, the resin component derived from the (P) layer and the resin component derived from the (Q) layer can be laminated using a multilayer die using an extruder. It can be multi-layered in a single stage and is economical.

In the release film for producing a printed circuit board of the present invention, the contact angle between the film surface of the outermost surface layer and water droplets is preferably 80 ° or more. From the viewpoint of releasability and moisture absorption resistance, it is 80 ° or more, preferably 85 ° or more, more preferably 90 ° or more. Here, the measurement of the contact angle between the film surface and water droplets can be performed in a normal temperature (23 ° C.) atmosphere using, for example, a solid-liquid interface analysis device DropMaster (registered trademark) manufactured by Kyowa Interface Science Co., Ltd.
The printed circuit board in the release film for producing a printed circuit board of the present invention includes a rigid type printed circuit board represented by an epoxy resin and a flexible printed circuit board represented by polyimide. Recently, especially in a flexible printed circuit board, the required specifications for outgas and contamination such as a mobile phone and a hard disk drive (HDD) have become considerably high, and the release film of the present invention is also from the viewpoint of excellent stain resistance. A flexible printed circuit board is more preferable.

  The release film for producing a printed circuit board of the present invention thus obtained is excellent in releasability, stain resistance and moisture absorption resistance, has a small thermal shrinkage, hardly wrinkles the printed circuit board product, and the release film itself. It is also difficult to wrinkle. Furthermore, it is excellent in followability, adhesive extruding property, adhesion between multilayer films, and slip property between films, and is a release film suitable for production of printed circuit boards, particularly flexible printed circuit boards.

The present invention will be described below based on examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
Production Example 1: Production Example of Polyphenylene Ether (PPE-1) Powdery poly (2,6-dimethyl-1,4-phenylene ether having a reduced viscosity of 0.42 obtained by oxidative polymerization of 2,6-dimethylphenol ).
Production Example 2: Production Example of Liquid Crystalline Polyester (LCP-1) In a nitrogen atmosphere, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, acetic anhydride was charged, heated, melted, and polycondensed to produce the following. A liquid crystal polyester (LCP-1) having the following theoretical structural formula was obtained. In addition, the component ratio of a composition represents molar ratio.

Production Example 3: Production Example of Liquid Crystalline Polyester (LCP-2) In a nitrogen atmosphere, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, hydroquinone, isophthalic acid, and acetic anhydride are charged, heated, melted, and polycondensed. As a result, a liquid crystal polyester having the following theoretical structural formula was obtained. In addition, the component ratio of a composition represents molar ratio.

Film formation and physical property evaluation of each resin composition were performed according to the following methods.
(1) Inflation Molding The obtained pellets were molded by extrusion using a tubular method using an extruder with a screw diameter of 50 mm set at a cylinder temperature of 290 ° C. and a cylindrical die temperature of 290 ° C. The pressure of the air to blow was set so that thickness might be set to 50 micrometers. In the case of a multilayer film, the pressure of air to be blown is adjusted and fused with a pinch roller to form a three-layer film structure with a thickness of (P) layer of 30 μm, (Q) layer of 150 μm, and (P) layer of 30 μm. Created to be.

(2) T-die extrusion molding The pellet obtained was discharged at a rate of 60 kg / hr and the thickness of the T-die slit using a vented single screw extruder with a screw diameter of 65 mm set at a cylinder temperature of 300 ° C and a T-die temperature of 300 ° C. Extrusion film molding was carried out by controlling the take-up speed so that the thickness was 0.15 mm, the die slit width was 650 mm, the rolling roller surface temperature was 130 ° C., and the thickness was 50 μm. When obtaining a multilayer film, a three-layer extruder is used, a feed block type three-layer T die is used, the total discharge amount is 60 kg / hr, the die slit width is 650 mm, the rolling roller surface temperature is 130 ° C., Extrusion film molding was carried out by controlling the take-up speed so that the film thickness was a three-layer film structure in which the (P) layer was 30 μm, the (Q) layer was 150 μm, and the (P) layer was 30 μm.

(3) Film thickness The film width is cut into a size of 500 mm and the length direction is cut into 200 mm. A total of 10 points were measured in the width direction, a total of 10 points on the upper side and the lower side, and the same measurement was carried out on another sheet. The thickness was measured at a total of 20 points to obtain an average value.
(4) Contact angle Using the solid-liquid interface analyzer DropMaster500 (registered trademark) manufactured by Kyowa Interface Science Co., Ltd., the film obtained in (1) and (2) above is fixed on the stage, One drop (2 μL) of distilled water was dropped on the film, the contact angle was measured, 10 points were measured, and the average value was taken. The atmosphere was normal temperature (23 degreeC).

(5) Releasability A 25 μm thick polyimide film (DuPont: Kapton 100H (registered trademark)) is used as a base film, and a 20 μm thick epoxy adhesive is used to form a 35 μm thick and 50 μm wide copper foil. A bonded copper-clad laminate (A) was obtained. Next, an epoxy adhesive having a flow start temperature of 80 ° C. was applied at a thickness of 20 μm on a polyimide film having a thickness of 25 μm (manufactured by DuPont: Kapton 100H (registered trademark)) to obtain a coverlay film (A). . The single-layer film having a thickness of 50 μm obtained in the above (1) or (2) was used as a release film (c). The films are stacked in the order of (C), (A), (B), and (C) so that the epoxy adhesive layer of (A) is in contact with the copper foil side of (A), and 190 ° C., 50 kgf / cm ^2. Hot pressing was performed for 1 minute to obtain a flexible printed circuit board. After the heat press, when the release film (c) and the polyimide film (a, i) were peeled off, the releasability was determined according to the following criteria.
Release from the substrate surface is “to FPC”, and (a) and (b) are exposed from the land part (electrode hole) and the release from the copper foil is “to adhesive / copper foil” It was.
○: It peels without any resistance.
Δ: There is a little resistance when peeling.
X: Adhered and not easily peeled off.
After peeling (in the case of x, it was peeled off forcibly), it was confirmed whether or not the release film was torn.

(6) Heat shrinkage rate The release film obtained in the above (1) and (2) was cut into a size of 150 mm × 150 mm so that each piece was parallel to MD and TD, and set to 190 ° C. Set in the oven for 5 minutes, remove and cool. The dimension before and after heating was measured for each of MD and TD, and determined according to the following formula.
Thermal contraction rate (%) = (length of side before heating−length of side after heating) / (length of side before heating) × 100
Here, MD is the direction in which the resin flows from the die of an inflation extrusion molding machine or a T-die extrusion molding machine, and TD indicates a direction perpendicular to MD.

(7) FPC (flexible printed circuit board) wrinkle Press in the same manner as in (3) above except that a polyimide film (DuPont: Kapton 50H (registered trademark)) with a thickness of 12.5 μm × 150 × 250 mm was used. The test was carried out, the obtained FPC was taken out, and the presence or absence of wrinkles of the FPC was confirmed.
(8) Bleed out 1
A 125 μm-thick polyimide film (manufactured by DuPont: Kapton 500H (registered trademark)) was sandwiched between the release films obtained in the above (1) or (2), and the condition was 190 ° C., 30 kgf / cm ² , for 5 minutes. Hot press. Then, after removing the release film, a line is written on the polyimide film surface that has been in contact with the release film with water-based magic (pen tip thickness: about 1.5 mm) and left for 5 minutes. The repellency was visually observed, and the bleeding out property was judged according to the following criteria.
○: Magic ink is not repelled.
X: The state where the magic ink was repelled.

(9) Bleed out 2
A polyimide film having a thickness of 125 μm (manufactured by DuPont: Kapton 500H (registered trademark)) was bar-coated with an epoxy adhesive having a thickness of 20 μm and cured at 50 ° C. for 2 hours to prepare an adhesive-coated polyimide film. The release film obtained in (1) or (2) above was overlaid on the adhesive-coated surface of this film, and hot-pressed at 190 ° C. and 30 kgf / cm ² for 5 minutes. Then, the release film was peeled off, and the contact angle on the adhesive-coated surface side of polyimide was measured according to the method (4) above. On the other hand, the adhesive-coated polyimide film as a blank was cured at 190 ° C. for 5 minutes without applying pressure, and after cooling, the contact angle on the surface was measured to be 58 °. Therefore, compared with the contact angle (58 °) of the blank, it was determined that there was some bleed out on the polyimide side as the difference increased.

(10) Hygroscopic resistance The film obtained in the above (1) or (2) is cut into a size of 100 × 190 mm square, and a constant temperature and humidity chamber (PL-3FP manufactured by Tabai Espec Co., Ltd.) is used. After exposure to a warm and humid environment of 95% relative humidity for 48 hours, the weight increase rate (Δw) was determined according to the following formula. The average value of each two films was taken.
Weight increase rate (Δw) (%) = (w ₁ −w ₀ ) / w ₀ × 100
(W ₁ : film weight (g) after warming and humidification, w ₀ : weight of film after drying in a hot air dryer at 100 ° C. for 2 hours and then cooling to room temperature in a desiccator (g ))
A smaller weight increase rate (Δw) means better moisture absorption resistance.

(11) Heat resistance An injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd.] in which the obtained pellets were set to a cylinder temperature of 320/330/320/310 ° C, a firing speed of 85%, and a mold temperature of 90 ° C. ] Was used to form. However, for Comparative Example 1 and Comparative Example 2, the cylinder set temperature was all set at 280 ° C. It was molded into an ASTM tanzania test piece having a thickness of 3.2 mm, a length of 127 mm, and a width of 12.7 mm. Using the obtained molded piece, the deflection temperature under a load of 1.82 MPa was measured according to ASTM D648.
(12) Rigidity Using the same test piece as in (11) above, using an autograph (AG-5000, manufactured by Shimadzu Corporation), in accordance with ASTM D790, in a temperature atmosphere of 23 ° C., flexural modulus The bending strength was measured.

[Example 1]
Top feed side barrel temperature of polyphenylene ether (PPE-1), liquid crystal polyester (LCP-1) and zinc oxide (ZnO, Ginbao-A, manufactured by Toho Zinc Co., Ltd.) in the proportions (parts by weight) shown in Table 1. The mixture was melt-kneaded using a twin-screw extruder equipped with a vent port (ZSK-25; manufactured by WERNER & PFLIDEER) having a barrel temperature and a die head temperature all set at 310 ° C. Using this pellet, a film having an average thickness of 51 μm was obtained by T-die extrusion shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 184 ° C. The flexural modulus was 2,670 MPa.

[Example 2]
(A) As a component, it carries out similarly to Example 1 except having mix | blended each component by the ratio (weight part) shown in Table 1 using polystyrene (GP, PS Japan Co., Ltd. product, G9305). A pellet was obtained. A film having an average thickness of 50 μm was obtained by T-die extrusion shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 167 ° C. The flexural modulus was 2,740 MPa.

[Example 3]
As component (B), LCP-2 was used, and as liquid component (E), liquid paraffin (Wax 1, manufactured by ExxonMobil Co., Ltd., Christol N352, colorless liquid at room temperature) was used. A pellet was obtained in the same manner as in Example 2 except that it was blended in (part by weight). A film having an average thickness of 49 μm was obtained by T-die extrusion shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 168 ° C. The flexural modulus was 2,750 MPa.

[Example 4]
(A) As a component, high impact polystyrene (HIPS, manufactured by PS Japan Co., Ltd., H9405) was used, and instead of wax 1, polyethylene wax (wax 2, manufactured by Mitsui Chemicals, Mitsui High Wax (registered trademark)), 405MP, white solid at room temperature), and the same procedure as in Example 3 was carried out except that each component was blended in the proportions (parts by weight) shown in Table 1 to obtain pellets. A film having an average thickness of 50 μm was obtained by T-die extrusion shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 163 ° C. The flexural modulus was 2,820 MPa.

[Example 5]
Instead of zinc oxide, magnesium hydroxide (Mg (OH) ₂ , special grade, manufactured by Wako Pure Chemical Industries, Ltd.) is used as the component (C), and other components are blended in the proportions shown in Table 1. Was carried out in the same manner as in Example 3 to obtain pellets. A film having an average thickness of 52 μm was obtained by T-die extrusion as shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 158 ° C. The bending elastic modulus was 2,600 MPa.

[Example 6]
As other components other than the components (A) to (E), a partially hydrogenated polymer of a block copolymer of an aromatic vinyl compound and a conjugated diene compound (SEBS1, manufactured by Asahi Kasei Chemicals Corporation, Tuftec H1272 (registered trademark)) (SEBS2, manufactured by Asahi Kasei Chemicals Co., Ltd., Tuftec H1041 (registered trademark)), except that the other components are blended in the proportions shown in Table 1 to obtain pellets. It was. A film having an average thickness of 60 μm was obtained by the inflation molding shown in (1) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 150 ° C. The flexural modulus was 2,300 MPa.

[Example 7]
As a component (D) instead of component (C), an amino group-containing silane compound (silane 1, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, KBM-602, Shin-Etsu Chemical Co., Ltd.) ), And other components were blended in the proportions shown in Table 1 to obtain pellets in the same manner as in Example 6. A film having an average thickness of 40 μm was obtained by the inflation molding shown in (1) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 176 ° C. The flexural modulus was 2,740 MPa.

[ Reference Example 1 ]
As a resin composition containing PPE, a high heat-resistant modified PPE resin (modified PPE, manufactured by Asahi Kasei Chemicals Co., Ltd., Zylon X9102 (registered trademark)), which is an alloy of polyphenylene ether and polystyrene resin, is used (1) A film having an average thickness of 40 μm was obtained by the inflation molding shown in FIG. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 159 ° C. The bending elastic modulus was 2,360 MPa.

[ Reference Example 2 ]
(A) About the component and other components, except having mix | blended in the ratio shown in Table 1, it implemented similarly to Example 1 and obtained the pellet. A film having an average thickness of 50 μm was obtained by the inflation molding shown in (1) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 143 ° C. The flexural modulus was 2,100 MPa.

[Comparative Example 1]
Using a poly-4-methyl-1-pentene resin (PMP, RT18, TPX (registered trademark), manufactured by Mitsui Chemicals, Inc.) as a pellet, a film having an average thickness of 51 μm was formed by the inflation molding shown in (1). Obtained. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 100 ° C. The flexural modulus was 1,280 MPa.

[Comparative Example 2]
A polyethylene terephthalate resin (PET, NEH2050, manufactured by Unitika Ltd.) was used as a pellet, and a film having an average thickness of 50 μm was obtained by T-die extrusion shown in (2). The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 75 ° C. The flexural modulus was 2,420 MPa.

[Comparative Example 3]
A pellet was obtained in the same manner as in Example 1 except that the components (A) to (C) were blended in the proportions shown in Table 1. A film having an average thickness of 50 μm was obtained by T-die extrusion shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 172 ° C. The bending elastic modulus was 5,100 MPa.

[Example 8 ]
A pellet was obtained in the same manner as in Example 1 except that the components (A), (B), (C), and (E) were blended in the proportions shown in Table 1. A film having an average thickness of 52 μm was obtained by T-die extrusion as shown in (2) above. The film was evaluated according to the method shown above. The results are shown in Table 1. The deflection temperature under load was 151 ° C. The flexural modulus was 2,400 MPa.

From the above, the film comprising the resin layer (P) containing 50% by weight or more of the polyphenylene ether resin of the present invention is excellent in releasability, small in heat shrinkage, hardly wrinkled on the printed circuit board product, and Since the release film itself is not easily wrinkled and has no bleed-out, it can be seen that the release film is excellent in stain resistance and moisture absorption resistance, and is suitable for manufacturing a flexible printed circuit board.
Next, a release film for producing a printed board having a multilayer structure, which is a second invention, will be described.

(13) Followability The film is placed on a brass plate with a groove of 30 μm depth, pressed using a hot press under the conditions of 180 ° C., 30 kg / cm ² for 3 minutes, and the bite into the groove is visually observed. The following was judged based on the following criteria.
○: The groove transferability is very good.
X: The transferability of the groove is poor or wrinkles occur around the groove.

(14) Adhesive protrusion In the evaluation of releasability in (5) above, the amount of adhesive protruding inside after pressing against a land (hole for electrode) having a diameter of 1.5 mm was measured with an optical microscope. And the protruding property of the adhesive was evaluated based on the following criteria.
◯: When the amount of adhesive protruding is 0.08 mm or less.
(Triangle | delta): When the amount which the adhesive protrudes exceeds 0.08 mm and is 0.15 mm or less.
X: When the amount of adhesive protruding exceeds 0.15 mm.
(15) P-Q interlayer adhesive strength ○: P layer and Q layer films are not peeled off.
X: P layer and Q layer easily peel off or do not adhere at all.

(16) Slip property After stacking two multilayer films and pressing them with a press machine at room temperature, 5 kg / cm ² and 15 seconds, only the upper layer film is slid, and the slip property with the lower layer film is as follows. Judgment criteria were used. Conducted 3 times.
○: In all three times, only the upper film could be easily slid without sticking to the lower film.
X: It stuck to the lower film at least once or more, and only the upper film could not be slid.

Production Example 4: Production Example 1 (P-i) of Resin Layer (P)
The pellet obtained in Example 1 was used as it was.
Production Example 5: Production Example 2 (P-ii) of Resin Layer (P)
The pellet obtained in Example 2 was used as it was.
Production Example 6: Production Example 3 of the resin layer (P) (P-iii, P-iv, Pv)
Pellets were obtained in the same manner as in Example 1 except that the proportions shown in Table 2 were blended.
Production Example 7: Production Example 4 (P-vi) of Resin Layer (P)
Asahi Kasei Chemicals Co., Ltd. Xylon X9102 (registered trademark) was used.

Production Example 8: Production Example 5 (P-vii) of Resin Layer (P)
2 parts of maleic anhydride (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), 80 parts of PPE-1, 15 parts of high impact polystyrene (H9405, manufactured by PS Japan), polystyrene (685, manufactured by PS Japan) ) 5 parts was blended and carried out in the same manner as in Production Example 4 to obtain a polyphenylene ether-based resin composition functionalized with maleic anhydride.
Production Example 9: Production Example of Partially Hydrogenated Polymer (SEBS-i) of Block Copolymer of Aromatic Vinyl Compound and Conjugated Diene Compound Polystyrene-hydrogenated polybutadiene-polystyrene structure having a bound styrene content of 35% Partial water of a block copolymer having a number average molecular weight of 62,000, a molecular weight distribution of 1.05, a 1,2-vinyl bond amount of the polybutadiene before hydrogenation of 38%, and a hydrogenation rate of the polybutadiene part of 99.9% An additive polymer was synthesized.

Production Example 10: Production Example of Partially Hydrogenated Polymer (SEBS-ii) of Block Copolymer of Aromatic Vinyl Compound and Conjugated Diene Compound Polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 60% Partial water of the block copolymer having a number average molecular weight of 89,000, a molecular weight distribution of 1.08, a 1,2-vinyl bond content of the polybutadiene before hydrogenation of 38%, and a hydrogenation rate of the polybutadiene part of 99.8% An additive polymer was synthesized.

Production Example 11 Production Example of Partially Hydrogenated Polymer (SEBS-iii) of Block Copolymer of Aromatic Vinyl Compound and Conjugated Diene Compound According to the method described in JP-A-63-99257, 1,3-dimethyl- It has a structure of polystyrene-hydrogenated polybutadiene-polystyrene using 2-imidazolidinone, 8% bonded styrene, number average molecular weight 51,000, molecular weight distribution 1.04, 1,2-vinyl bond of polybutadiene A block copolymer having an amino group at the end, the amount of which was 38%, was obtained, and a hydrogenated hydrogenation rate of the polybutadiene portion was synthesized as a block copolymer partially hydrogenated polymer by 99.8%.

Production Example 12: Production Example of Partially Hydrogenated Polymer (SEBS-iv) of Block Copolymer of Aromatic Vinyl Compound and Conjugated Diene Compound Polystyrene-hydrogenated polybutadiene-polystyrene structure with 3% bound styrene content Partial water of a block copolymer having a number average molecular weight of 52,000, a molecular weight distribution of 1.05, a 1,2-vinyl bond amount of polybutadiene before hydrogenation of 38%, and a hydrogenation rate of polybutadiene part of 99.9% An additive polymer was synthesized.
Production Example 13: Production Example of Partially Hydrogenated Polymer (SEBS-v) of Block Copolymer of Aromatic Vinyl Compound and Conjugated Diene Compound Polystyrene-hydrogenated polybutadiene-polystyrene structure having a bound styrene content of 70% Partial water of block copolymer having a number average molecular weight of 82,000, molecular weight distribution of 1.05, 1,2-vinyl bond content of polybutadiene before hydrogenation is 38%, and hydrogenation rate of polybutadiene part is 99.9% An additive polymer was synthesized.

[Example 11]
Using P-i as the (P) layer and SEBS-i as the (Q) layer, a multilayer film was obtained by the extrusion molding method using the T-die shown in (2) above. Using this as a release film, the film was evaluated according to the method shown above. The results are shown in Table 3.

[Example 12]
A multilayer film was obtained in the same manner as in Example 11 except that P-ii was used as the (P) layer, and the film was evaluated according to the method described above. The results are shown in Table 3.

[Example 13]
The film was evaluated in the same manner as in Example 11 except that P-iii was used as the (P) layer, and a multilayer film was obtained by the extrusion molding method by inflation shown in (1) above. It was shown in 3.

[Example 14]
(P) Except having used P-iv as a layer, the multilayer film was obtained similarly to Example 11 and the film was evaluated according to the method shown above. The results are shown in Table 3.

[Example 15]
(P) Except having used Pv as a layer, the multilayer film was obtained similarly to Example 11 and the film was evaluated according to the method shown above. The results are shown in Table 3.

[Example 16]
A multilayer film was obtained in the same manner as in Example 11 except that SEBS-ii was used as the (Q) layer, and the film was evaluated according to the method described above. The results are shown in Table 3.

[Example 17]
A multilayer film was obtained in the same manner as in Example 11 except that P-vi was used as the (P) layer and SEBS-ii was used as the (Q) layer, and the film was evaluated according to the method shown above. did. The results are shown in Table 3.

[Example 18]
A multilayer film was obtained in the same manner as in Example 11 except that P-vii was used as the (P) layer and SEBS-iii was used as the (Q) layer, and the film was evaluated according to the method shown above. did. The results are shown in Table 3.

[Example 19]
As the (Q) layer, an ethylene-vinyl acetate copolymer (EVA-1, manufactured by Asahi Kasei Chemicals Corporation, Suntec EF0925 (registered trademark), VA content 9% by weight, MFR = 2.5 g / 10 min) was used. With the first roll set at 165 ° C., each of the P-i monolayer films obtained by the T-die method of (2) was fed from above and below the T-die, and EVA-1 resin was poured from the T-die in a molten state. A film having a multilayer structure was obtained by dry lamination. The thickness of the P / Q / P layer was 30/150/30 μm.

[Example 20]
A film having a multilayer structure was obtained by the dry lamination method in the same manner as in Example 19 except that P-iv was used as the (P) layer. The thickness of the P / Q / P layer was 25/150/25 μm.

[Example 21]
(Q) The same procedure as in Example 11 was performed except that SEBS-iv was used as the layer. The interlayer adhesion of PQ was x. It peeled off easily.

[Example 22]
(Q) The same procedure as in Example 11 was performed except that SEBS-v was used as the layer. Followability was x. The protruding property of the adhesive was Δ.

[Comparative Example 4]
(P) A poly-4-methyl-1-pentene resin (PMP, RT18, TPX (registered trademark), manufactured by Mitsui Chemicals, Inc.) was used as the layer, and the inflation molding shown in (1) was performed. Obtained the multilayer film similarly to Example 11, and used this as a release film, and evaluated the film according to the method shown above. The results are shown in Table 3. Since the PQ layer did not adhere well, the followability and slip property could not be evaluated.

[Comparative Example 5]
As the (P) layer, a multilayer film was obtained in the same manner as in Example 11 except that polyethylene terephthalate resin (PET, NEH2050, manufactured by Unitika Ltd.) was used, and this was used as a release film. The film was evaluated according to the method. The results are shown in Table 3. Since the PQ layer did not adhere well, the followability and slip property could not be evaluated.

[Comparative Example 6]
As the (P) layer, a poly-4-methyl-1-pentene resin (PMP, RT18, TPX (registered trademark), manufactured by Mitsui Chemicals, Inc.) is used as a single layer release film without the (Q) layer. The film was evaluated according to the method shown above. The results are shown in Table 3.

  From the above, the multilayer film of the (P) layer containing the (A) polyphenylene ether resin and the (F) layer containing the (F) elastomer according to the present invention is excellent in releasability, followability, It can be seen that the adhesive has excellent protrusion properties, adhesion between multilayer films, and slip properties between films, and is suitable for production of printed circuit boards, particularly flexible printed circuit boards.

  The release film of the present invention is excellent in releasability, stain resistance and moisture absorption resistance, has a small thermal shrinkage, does not wrinkle printed circuit board products, and does not wrinkle the release film itself. It is a release film suitable for manufacturing printed circuit boards, particularly flexible printed circuit boards.

Claims (15)

  A release film for producing a printed circuit board comprising a resin layer (P) containing (A) 50 to 99.5 parts by weight of a polyphenylene ether resin and (B) 0.5 to 50 parts by weight of a liquid crystal polyester. A resin containing 0.1 to 10 parts by weight of a compound containing (C) an I-valent, II-valent, III-valent or IV-valent metal element with respect to a total of 100 parts by weight of the component (A) and the component (B) The release film for producing a printed circuit board according to claim 1 , comprising a layer (P). (C) The release film for producing a printed circuit board according to claim 2 , comprising a resin layer (P) in which the metal element of I, II, III, or IV is a Zn element and / or a Mg element. The component (A) and (B) total 100 parts by weight of components, according to claim 1 consisting of (D) a resin layer containing a silane compound 0.1-5 parts by weight (P) Release film for printed circuit board production. The release film for producing a printed circuit board according to claim 4 , wherein the silane compound comprises a resin layer (P) which is a silane compound having an amino group. The component (A) and (B) total 100 parts by weight of component, (E) any one of claims 1 to 5, comprising a resin layer containing a hydrocarbon-based wax 0.1-4 parts by weight (P) The release film for printed circuit board manufacture of description. A release film for producing a printed board having a single-layer structure, comprising the resin layer (P) according to any one of claims 1 to 6 . A release film for producing a printed board having a multilayer structure comprising the resin layer (P) according to any one of claims 1 to 6 and a layer (Q) containing (F) an elastomer. The release film for producing a printed circuit board according to claim 8 , wherein the elastomer (F) is a partially hydrogenated polymer of a block copolymer of (F1) an aromatic vinyl compound and a conjugated diene compound. The release film for producing a printed circuit board according to claim 9 , wherein the component (F1) is a partially hydrogenated polymer of a block copolymer having an aromatic vinyl compound bond amount of 5 wt% to 65 wt%. The release film for producing a printed circuit board according to claim 8 , wherein the elastomer (F) is a copolymer of (F2) ethylene and a vinyl ester compound. The mold release film for printed circuit board manufacture in any one of Claims 1-11 obtained by shape | molding by the extrusion tubular method. The mold release film for printed circuit board manufacture in any one of Claims 1-11 obtained by shape | molding by the T-die extrusion method. The release film for manufacturing a printed circuit board according to any one of claims 1 to 13 , wherein a contact angle between the film surface of the outermost surface layer and water droplets is 80 ° or more. The release film for producing a printed circuit board according to any one of claims 1 to 14 , wherein the printed circuit board is a flexible printed circuit board.