JP2008230168A - Laminated sheet and method for manufacturing conductive pattern sheet by using the laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet which has an anchor coat layer having high adhesive properties and high heat resistance and can appropriately be used in the manufacturing of a conductive pattern sheet, and a method for manufacturing the conductive pattern sheet using the laminated sheet. <P>SOLUTION: In the laminated sheet, a separator (1), an adhesive insulating layer (2a), an anchor coat layer (3), and an active energy ray-transmittable sheet-shaped support (4a) are successively laminated. The anchor coat layer (3) is formed of a resin composition (I) containing: a polyurethane resin (A) obtained by making a urethane pre-polymer (d) which is obtained by making a diol compound (a) having a carboxyl group, polyol (b) whose number average molecular mass is 5,000 to 8,000 and which is other than (a), and organic diisocyanate (c) react with one another, and has an isocyanate group at its end react with one another; and an epoxy group (B) having two or more epoxy groups. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a laminated sheet suitably used for producing a conductive pattern sheet, and a method for producing a conductive pattern sheet using the laminated sheet.
Specifically, the laminated sheet includes, as constituent materials, an adhesive layer that loses its adhesiveness upon irradiation with active energy rays, and an anchor coat layer that has high adhesion to the substrate and high heat resistance. Is.

Conductive pattern sheets are widely used in various fields.
For example, in order to block electromagnetic waves emitted from devices such as plasma display panels (PDP), a transparent sheet having a fine conductive pattern that does not hinder the display of images is used as an electromagnetic wave shielding sheet, and the plasma display panel (PDP) It is used suitably for formation of. In addition, a transparent electrode substrate formed in a desired pattern is used as a transparent electrode for applying a voltage to the liquid crystal for each pixel, which is a substrate sandwiching a liquid crystal of a liquid crystal display. Further, a printed wiring board such as a flexible printed wiring board has a desired conductive pattern, that is, a conductive circuit formed on a sheet-like support.

  The formation method of the conductive pattern sheet used in various fields is roughly divided into two types of methods, a subtractive method and an additive method. The subtractive method is a method of leaving a necessary conductive pattern by removing unnecessary portions from a conductive layer provided on the entire surface of a support. On the other hand, the additive method is a method in which only a necessary conductive pattern is formed on a support without providing a conductive layer in unnecessary portions.

As one of the additive methods, there is already a known technique in which a photosensitive pattern is exposed imagewise, and an electroless plating catalyst is imagewise deposited thereon to perform plating to obtain a conductive pattern (patent) Document 1: JP-A-53-88955, Patent Document 2: JP-A-53-88956).
However, in these methods, since the entire surface of the photosensitive layer is finally cured, after the curing, the photosensitive layer cannot be maintained with adhesion to a substrate such as polyester or polyimide, and peels off. It is difficult to use as it is as a member of a laminated structure composed of a photosensitive layer and a conductive pattern. Therefore, it has been proposed to provide an anchor coat layer between the base material and the light-sensitive layer to maintain the adhesion between the base material and the light-sensitive layer, but the anchor coat has sufficient adhesiveness and high heat resistance. The agent has not yet been developed (Patent Document 3: Japanese Patent No. 3825746).
JP-A-53-88955 JP-A-53-88956 Japanese Patent No. 3825746

  The present invention relates to a laminated sheet that has an anchor coat layer having high adhesion and high heat resistance and is suitably used for producing a conductive pattern sheet, and a method for producing a conductive pattern sheet using the laminated sheet. The purpose is to provide.

That is, the first invention is
The separator (1), the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a), which can lose the adhesiveness after being cured by active energy ray irradiation, are sequentially provided. A laminated sheet that is laminated,
The anchor coat layer (3)
Urethane prepolymer having an isocyanate group at the end, obtained by reacting a diol compound (a) having a carboxyl group, a polyol (b) other than (a) and an organic diisocyanate (c) having a number average molecular weight of 500 to 8000. A polyurethane polyurea resin (A) obtained by reacting (d) with a polyamino compound (e), and
The present invention relates to a laminated sheet characterized by being formed from a resin composition (I) containing an epoxy resin (B) having two or more epoxy groups.

In addition, the second invention,
The separator (1), the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a), which can lose the adhesiveness after being cured by active energy ray irradiation, are sequentially provided. A laminated sheet that is laminated,
The anchor coat layer (3)
A polyester resin (c4) having a hydroxyl group obtained by reacting the diol (c1) with a dibasic acid or dibasic acid anhydride (c2) or a dialkyl ester (c3) of a dibasic acid, and three in the molecule A polyester resin (C) obtained by reacting the above polybasic acid having a carboxyl group or its anhydride (c5), and
The present invention relates to a laminated sheet characterized by being formed from a resin composition (II) containing an epoxy resin (D) having two or more epoxy groups.

  The third invention relates to the laminated sheet of the first or second invention, wherein the separator (1) is an active energy ray permeable separator (1a).

In addition, the fourth invention is
From the active energy ray permeable separator (1a) side of the laminated sheet of the third invention, the adhesive insulating layer (2a) is irradiated with active energy rays in a pattern,
After forming a partially adhesive insulating layer (2b) having a pattern consisting of a cured part that has lost adhesiveness and an uncured part that has adhesiveness,
Removing the active energy ray permeable separator (1a);
The conductive powder (6) is brought into contact with the exposed surface of the partially adhesive insulating layer (2b), and the conductive powder (6) is applied to the uncured portion having adhesiveness in the partially adhesive insulating layer (2b). Remove the conductive powder (6) that is attached and in contact with the cured part that has lost its adhesiveness,
Next, the active energy ray-transmitting sheet-like support (4a) side of the laminated sheet is irradiated with active energy rays to cure the uncured portion of the partial adhesive insulating layer (2b) and to have no adhesiveness. While forming the layer (2c)
Fix the conductive powder (6) adhering to the uncured part to the insulating layer (2c),
The present invention relates to a method for producing a conductive pattern sheet, characterized in that a conductive pattern (7) made of conductive powder (6) is formed on an insulating layer (2c).

  Furthermore, the fifth invention relates to a method for producing a conductive pattern sheet according to the fourth invention, wherein metal plating is further performed on the conductive pattern (7).

  Furthermore, the sixth invention relates to a conductive pattern sheet obtained by the manufacturing method of the fourth or fifth invention.

According to the present invention, there is provided a laminated sheet that has an anchor coat layer having high adhesiveness and high heat resistance and is preferably used for producing a conductive pattern sheet, and a method for producing a conductive pattern sheet using the laminated sheet. Can now be offered.

First, the anchor coat layer (3) of the laminated sheet of the present invention will be described.
The anchor coat layer (3) is provided in the laminated sheet in order to enhance the adhesion between the insulating layer and the sheet-like support.
The anchor coat layer (3) includes a polyurethane polyurea resin (A) and a resin composition (I) containing an epoxy resin (B) having two or more epoxy groups,
Or
It is formed from a resin composition (II) containing a polyester resin (C) and an epoxy resin (D) having two or more epoxy groups.

The polyurethane polyurea resin (A) contained in the resin composition (I) is a diol compound (a) having a carboxyl group, a polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and an organic diisocyanate ( It is obtained by reacting a urethane prepolymer (d) having an isocyanate group at the terminal obtained by reacting c) with a polyamino compound (e).
Examples of the diol compound (a) having a carboxyl group include dimethylol alkanoic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolpentanoic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. In particular, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of reactivity and solubility.

  The polyol (b) other than (a) having a number average molecular weight of 500 to 8000 is a polyol other than the diol compound (a) having a carboxyl group, which is generally known as a polyol component constituting the polyurethane resin. The number average molecular weight (Mn) of the polyol (b) is appropriately determined in consideration of the heat resistance, adhesive strength, solubility and the like of the obtained polyurethane polyurea resin (A), and is preferably 1000 to 5000. When Mn is less than 500, the number of urethane bonds in the resulting polyurethane polyurea resin (A) increases too much, and the flexibility of the polymer skeleton tends to decrease and the adhesion to the insulating layer and the sheet-like support tends to decrease. In addition, when Mn exceeds 8000, the number of carboxyl groups derived from the diol compound (a) in the polyurethane polyurea resin (A) decreases. As a result, the reaction point with the epoxy resin decreases, so that the heat resistance of the obtained anchor coat layer tends to be lowered.

As the polyol (b) other than (a) having a number average molecular weight of 500 to 8000, various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols and the like can be used.
Examples of polyether polyols include polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran.

Polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, Saturated or unsaturated low molecular weight diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimer diol, and adipic acid, phthalic acid, isophthalic acid Reaction with dicarboxylic acids such as acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, or their anhydrides Po obtained And ester polyols,
Alkyl glycidyl ethers such as n-butyl glycidyl ether or 2-ethylhexyl glycidyl ether, or monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester and anhydrides of the above dicarboxylic acids containing hydroxyl groups such as alcohols Polyester polyols obtained by reacting in the presence of a compound,
Or the polyester polyol obtained by ring-opening-polymerizing a cyclic ester compound is mentioned.

Examples of polycarbonate polyols include:
1) A reaction product of glycol or bisphenol and a carbonate ester, or 2) a reaction product obtained by reacting glycol or bisphenol with phosgene in the presence of an alkali can be used.
Examples of the glycol used in the case of 1) or 2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1. , 8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, and cyclohexanediol.

Examples of the bisphenol used in the case of 1) or 2) include, for example, bisphenols such as bisphenol A and bisphenol F, and compounds obtained by adding alkylene oxides such as ethylene oxide or propylene oxide to these bisphenols. Is mentioned.
Examples of the carbonic acid ester used in the case 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

The various polyols exemplified as the polyol (b) other than (a) having a number average molecular weight of 500 to 8000 may be used alone or in combination of two or more.
Furthermore, within the range in which the performance of the resulting polyurethane polyurea resin (A) is not lost, the diol compound (a) having a carboxyl group, the polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and In reacting the organic diisocyanate (c), low molecular diols other than the diol compound (a) having a carboxyl group may be used in combination. Examples of the low-molecular diols that can be used in combination include various low-molecular diols having a number average molecular weight of 500 to 8000, which are used for producing a polyol (b) other than (a).

  When the urethane prepolymer (d) is synthesized, the diol compound (a) having a carboxyl group and the polyol (b) other than (a) having a number average molecular weight of 500 to 8000 are the number average molecular weight of 500 to 8000. It is preferably used in a ratio of 0.1 mol to 4.0 mol of the diol compound (a) having a carboxyl group with respect to 1 mol of the other polyol (b), It is more preferable to use at the ratio. (B) When the amount of (a) used per 1 mol is less than 0.1 mol, the epoxy group (B) and the crosslinkable carboxyl group are reduced, and the heat resistance of the anchor coat layer tends to be lowered. On the other hand, when the amount is more than 4.0 mol, the active energy ray-permeable sheet-like support (4a), the adhesive insulating layer (2a), and the insulating layer formed by curing the adhesive insulating layer ( The adhesiveness to 2c) tends to be reduced.

As the organic diisocyanate (c), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and the like.

Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and the like.

  The urethane prepolymer (d) having an isocyanate group at the terminal is reacted with a diol compound (a) having a carboxyl group, a polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and an organic diisocyanate (c). Is obtained. The conditions for synthesizing the urethane prepolymer (d) having an isocyanate group at the terminal are not particularly limited except that the isocyanate group becomes excessive, but the molar ratio of isocyanate group / hydroxyl group is 1.2 / 1. The diol compound (a) having a carboxyl group, the polyol (b) other than (a) and the organic diisocyanate (c) having a number average molecular weight of 500 to 8000 are reacted in such a ratio as to fall within the range of ˜3 / 1. It is preferable to make it. The reaction temperature is usually from room temperature to 120 ° C., but preferably from 60 to 100 ° C. from the viewpoint of production time and side reaction control.

The polyurethane polyurea resin (A) is obtained by reacting the urethane prepolymer (d) having an isocyanate group at the terminal with the polyamino compound (e).
Examples of the polyamino compound (e) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, 2- (2-aminoethylamino) ethanol, 2 Amines having a hydroxyl group such as -hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, and di-2-hydroxypropylethylenediamine can also be used. Of these, isophoronediamine is preferably used.

  When synthesizing the polyurethane polyurea resin (A) by reacting the urethane prepolymer (d) having an isocyanate group at the terminal with the polyamino compound (e), a reaction terminator can be used in combination to adjust the molecular weight. As the reaction terminator, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

  The conditions for reacting the urethane prepolymer (d) having an isocyanate group at the terminal, the polyamino compound (e) and, if necessary, the reaction terminator are not particularly limited, but the isocyanate group possessed by the urethane prepolymer (d) It is preferable that the molar ratio of the total of the amino groups in the polyamino compound (e) and the reaction terminator is in the range of 0.5 to 1.3. When the molar ratio is less than 0.5, the heat resistance of the anchor coat layer tends to be insufficient, and when it exceeds 1.3, the polyamino compound (e) and / or the reaction terminator remains unreacted. It remains and the odor tends to remain.

Solvents used when synthesizing the polyurethane polyurea resin (A) include aromatic solvents such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, isopropanol and n-butanol, acetone, methyl ethyl ketone and methyl isobutyl. Examples include ketone solvents such as ketones and ester solvents such as ethyl acetate and butyl acetate. These solvent can be used individually by 1 type or in mixture of 2 or more types.
It is preferable that the weight average molecular weight of the obtained polyurethane polyurea resin (A) exists in the range of 5000-100000. When the weight average molecular weight is less than 5000, the heat resistance of the anchor coat layer tends to be inferior, and when it exceeds 100,000, the adhesion of the anchor coat layer tends to be lowered.

The epoxy resin (B) contained in the resin composition (I) is a resin having two or more epoxy groups, and may be liquid or solid.
As the epoxy resin (B), bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, terpene type epoxy resin, tris (glycidyl) Glycidyl ether type epoxy resins such as oxyphenyl) methane and tetrakis (glycidyloxyphenyl) ethane, Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, Tetrabromobisphenol A type epoxy resin, Cresol novolac type epoxy resin, Phenol novolak type epoxy resin Examples thereof include resins, α-naphthol novolac type epoxy resins, brominated phenol novolac type epoxy resins and the like. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a tetrakis (glycidyloxyphenyl) ethane type epoxy resin from the viewpoint of high adhesion and heat resistance.

In the resin composition (I) used in the present invention, the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is 3 parts by weight of the epoxy resin (B) 3 with respect to 100 parts by weight of the polyurethane polyurea resin (A). It is preferable that it is -200 weight part, and it is more preferable that it is 5-100 weight part. (A) When (B) is less than 3 parts by weight with respect to 100 parts by weight, the heat resistance of the anchor coat layer tends to be low. On the other hand, if the amount of (B) is more than 200 parts by weight, the adhesion of the anchor coat layer tends to decrease. The resin composition (I) has a range that does not impair the performance such as adhesion, heat resistance, and bending resistance. Thus, a phenol resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, a polyamide resin, a polyimide resin, and the like can be contained.

Next, the resin composition (II) used in the present invention will be described.
Resin composition (II) contains a polyester resin (C) and an epoxy resin (D).

Polyester resin (C) is a polyester resin (c4) having a hydroxyl group obtained by reacting diol (c1) with dibasic acid or dibasic acid anhydride (c2) or dialkyl ester (c3) of dibasic acid. And a polybasic acid having 3 or more carboxyl groups in the molecule or its anhydride (c5).
Examples of the diol (c1) used for obtaining the polyester resin (c4) having a hydroxyl group include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-diethyl-1,3-propanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, 3- Ethyl to methyl-1,5-pentanediol, bisphenol A or bisphenol F Aliphatic dihydric alcohols such as oxides and propylene oxide added, xylene glycol, hydrogenated bisphenol A, and the like can be mentioned. Can do.

Examples of the dibasic acid or dibasic acid anhydride (c2) to be reacted with the diol (c1) include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and anhydrides thereof.
Examples of the aromatic dicarboxylic acid and its anhydride include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, and (phthalic anhydride) phthalic acid. Combined with phthalic anhydride, it is expressed as “(phthalic anhydride)”. The same applies below. ].
Examples of the alicyclic dicarboxylic acid and its anhydride include tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, 1,4-cyclohexanedicarboxylic acid, and the like.
Examples of the aliphatic dicarboxylic acid and its anhydride include (anhydrous) succinic acid, fumaric acid, (anhydrous) maleic acid, adipic acid, sebacic acid, azelaic acid, and hymic acid.
Examples of the dialkyl ester (c3) of the dibasic acid to be reacted with the diol (c1) include an esterified product of the dibasic acid and an alkyl alcohol having 1 to 18 carbon atoms. Examples of the alkyl alcohol having 1 to 18 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, and acetylisopropyl alcohol. , Neohexyl alcohol, isohexyl alcohol, n-hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, octadecyl alcohol and the like.
Preferred compounds as the dialkyl ester (c3) of dibasic acid are dimethylphthalic acid and dimethylisophthalic acid.
The dibasic acid or dibasic acid anhydride (c2) and the dialkyl ester (c3) of the dibasic acid can be appropriately selected from these in consideration of the physical properties of the obtained anchor coat layer.

The polyester resin (C) is obtained by reacting a polyester resin (c4) having a hydroxyl group with a polybasic acid having 3 or more carboxyl groups in the molecule or an anhydride (c5) thereof.
Examples of the polybasic acid having three or more carboxyl groups in the molecule or its anhydride (c5) include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, ethylene glycol bistrimellitic dianhydride, and the like. .
The ratio between the polyester resin having a hydroxyl group (c4) and the polybasic acid having 3 or more carboxyl groups in the molecule or its anhydride (c5) is appropriately determined in consideration of the molecular weight and acid value of both. However, the polyester resin (C) obtained by reacting both has an acid value of 5 to 40 mg KOH / g, a number average molecular weight of 10,000 to 40,000, and a glass transition temperature of 10 to 50 ° C. It is preferable to react.

  As described above, the polyester resin (C) preferably has an acid value of 5 to 40 mgKOH / g, and more preferably 10 to 30 mgKOH / g. When the acid value is less than 5 mgKOH / g, the epoxy resin (D) and the crosslinkable carboxyl group are reduced, and the heat resistance of the anchor coat layer tends to be lowered. On the other hand, when the acid value exceeds 40 mgKOH / g, the flexibility of the anchor coat layer tends to decrease.

  Moreover, it is preferable that it is 10000-40000, and, as for the number average molecular weight (Mn) of a polyester resin (C), it is more preferable that it is 15000-30000. When the number average molecular weight (Mn) is less than 10,000, the heat resistance and flexibility of the anchor coat layer tend to decrease. On the other hand, when the number average molecular weight (Mn) exceeds 40000, the solubility in the solvent and the coating property are remarkably decreased. It becomes difficult.

  Moreover, it is preferable that the glass transition temperature of a polyester resin (C) is 10-50 degreeC, and it is more preferable that it is 15-45 degreeC. When the glass transition temperature is less than 10 ° C., the heat resistance of the anchor coat layer tends to decrease, whereas when it exceeds 50 ° C., the flexibility of the anchor coat layer tends to decrease.

  As the epoxy resin (D) having two or more epoxy groups contained in the resin composition (II), the same one as the epoxy resin (B) can be used. Among these, from the viewpoint of heat resistance, it is preferable to use a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or a tetrakis (glycidyloxyphenyl) ethane type epoxy resin.

  In addition, the resin composition (II) includes phenolic resins, silicone resins, urea resins, acrylic resins, polyester resins, polyamides as long as the performance such as adhesion, heat resistance, and flex resistance is not impaired. Resin, polyimide resin and the like can be contained.

Resin composition (I) and resin composition (II) include a reaction between polyurethane polyurea resin (A) and epoxy resin (B), a reaction between polyester resin (C) and epoxy resin (D), and epoxy. For the purpose of promoting the reaction between the resins (B) or the epoxy resins (D), a curing accelerator and a curing agent can be contained.
As the curing accelerator, tertiary amine compounds, phosphine compounds, imidazole compounds and the like can be used, and as the curing agent, dicyandiamide, carboxylic acid hydrazide, acid anhydrides and the like can be used.
Among the curing accelerators, the tertiary amine compounds include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, 1,5-diazabicyclo (4.3.0) nonene-5. Etc. Examples of the phosphine compound include triphenylphosphine and tributylphosphine. Examples of imidazole compounds include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenylimidazole. Includes a latent curing accelerator with improved storage stability such as a type in which an imidazole compound and an epoxy resin are reacted to insolubilize in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule.

Examples of the carboxylic acid hydrazide as the curing agent include succinic acid hydrazide and adipic acid hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride and trimellitic anhydride.
As these curing accelerators or curing agents, two or more types may be used in combination, respectively, and the total amount used (including the case where only one of the curing accelerator or the curing agent is used) is an epoxy. It is preferable that it is the range of 0.1-30 weight part with respect to 100 weight part of resin (B) or an epoxy resin (D).

The anchor coat layer formed from the resin composition (I) or the resin composition (II) is excellent in transparency and can easily transmit active energy rays such as ultraviolet rays and electron beams.
In addition, the resin composition (I) and the resin composition (II) include silane coupling agents, antioxidants, pigments, dyes, as long as the adhesion, heat resistance, transparency, and the like of the anchor coat layer are not reduced. You may add tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, a flame retardant, etc.

Next, the separator (1) used in the present invention will be described.
The separator (1) is made of a plastic film such as polyethylene terephthalate (PET), biaxially stretched polypropylene or polyethylene, or paper as a base material, and at least one surface thereof is peeled off with silicon or a fluorine compound. is there.
In the present invention, the separator (1) is preferably an active energy ray permeable separator (1a) such as an ultraviolet ray or an electron beam. Particularly preferred is a base made of a colorless and transparent plastic film.

Next, the adhesive insulating layer (2a) will be described.
The adhesive insulating layer (2a) has an adhesive property before being cured, but is an insulating layer that can be cured by irradiation with active energy rays and lose its adhesive property. An insulating layer (2c) that does not have a film is formed.
The pressure-sensitive adhesive layer (2a) used in the present invention can be formed using a loss-of-stick type pressure-sensitive adhesive that is cured by irradiation with an active energy ray and loses the pressure-sensitive adhesive property.
Examples of the active energy rays include chemically active rays such as ultraviolet rays and electron beams. In the present invention, ultraviolet rays are preferably used.
As the adhesive loss-type pressure-sensitive adhesive, those containing a viscoelastic polymer having no ultraviolet curable property, an ultraviolet curable compound and a photopolymerization initiator are suitably used. Moreover, the compound which can react with the functional group which a viscoelastic copolymer has can be included as a hardening | curing agent.
In addition, silane coupling agents, antioxidants, pigments, dyes, tackifier resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, as long as the adhesiveness and heat resistance of the adhesive insulating layer are not deteriorated. You may add a filler, a flame retardant, etc.

Examples of the viscoelastic polymer in the loss-of-adhesion-type pressure-sensitive adhesive include acrylic resins, urethane resins, polyester-based resins, natural and synthetic rubbers, and silicone-based resins that are conventionally used for general pressure-sensitive adhesives.
Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, acetophenone dimethyl ketal, 2, Examples include 4-diethyl oxanson, 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, bisimidazole, β-chloranthraquinone, and the like.

As an ultraviolet curable compound, the monomer and oligomer which harden | cure by ultraviolet irradiation in presence of a photoinitiator are mentioned. These preferably have two or more acryloyl groups or methacryloyl groups in the molecule.
Examples of the monomer include 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, and the like.
Examples of the oligomer include urethane acrylate oligomers.
Urethane acrylate oligomers include polyols such as polyester polyols and polyether polyols and organic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene. A terminal isocyanate prepolymer obtained by reacting diisocyanate, diphenylmethane-4,4-diisocyanate, etc., with an acrylate or methacrylate having a hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, polyethylene glycol acrylate, Those obtained by reacting polyethylene glycol methacrylate, pentaerythritol triacrylate and the like can be used. The number average molecular weight of the urethane acrylate oligomer is preferably 500 to 30,000, more preferably 1,000 to 20,000. The urethane acrylate oligomer preferably has 2 to 10 acryloyl groups or methacryloyl groups, more preferably 4 to 10 and even more preferably 6 to 10.

Next, the active energy ray-permeable sheet-like support (4a) [hereinafter also simply referred to as “sheet-like support (4a)” used in the present invention. ] Will be described.
The sheet-like support (4a) functions as a support for the laminated sheet of the present invention,
It is important that the active energy ray can be transmitted, and various plastic films can be preferably used.
As the plastic film, for example, a polyester film made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.,
Polyolefin film made of polyethylene, polypropylene, polystyrene, ethylene / vinyl acetate copolymer (EVA), etc.,
In addition to vinyl films made of polyvinyl chloride, polyvinylidene chloride, etc., polysulfone, polyethersulfone, polyphenylene sulfide, polycarbonate, polyphenylene ether, polyetheretherketone, polytetrafluoroethylene, polyamide, polyimide, acrylic resin, cyclohexane The film formed from an olefin resin is mentioned.
The thickness of the sheet-like support (4a) can be appropriately selected according to the field / use in which the conductive pattern sheet obtained using the laminated sheet of the present invention is used.

Next, the manufacturing method of the lamination sheet of this invention and the manufacturing method of the electroconductive pattern sheet which uses the said lamination sheet are demonstrated based on drawing.
FIG. 1 is a schematic cross-sectional view showing one embodiment of a method for producing a conductive pattern sheet, using the laminated sheet of the present invention.
As shown in FIG. 1 [1], the anchor coat layer (3) provided on the active energy ray-permeable sheet-like support (4a) can be cured by irradiation with active energy rays, and is adhesive before curing. A laminate formed by laminating an adhesive insulating layer (2a) and an active energy ray transmissive separator (1a) covering the entire surface of the adhesive insulating layer (2a), which can lose adhesiveness after curing. A sheet (10) is obtained.
Such a laminated sheet (10) comprises a resin composition (I) or a resin composition (II) capable of forming the anchor coat layer (3) on the entire surface of one surface of the sheet-like support (4a). Apply, dry and cure as necessary, and apply a loss-of-adhesive adhesive that can form an adhesive insulating layer (2a) on the entire surface of the formed anchor coat layer (3). Accordingly, the entire surface of the adhesive insulating layer (2a) thus formed can be obtained by coating the entire surface of the adhesive insulating layer (2a) with the release treatment surface of the separator (1a).
Alternatively, the laminated sheet (10) is coated with a loss-of-adhesion-type pressure-sensitive adhesive that can form the adhesive insulating layer (2a) on the entire surface of the release treatment surface of the active energy permeable separator (1a). A resin composition capable of forming an anchor coat layer (3) is coated on the adhesive insulating layer (2a) which is dried and further formed, and dried and cured as necessary. It can also be obtained by coating the surface of the layer (3) with a sheet-like support (4a).
Alternatively, the laminated sheet (10) is coated with the resin composition (I) or the resin composition (II) capable of forming the anchor coat layer (3) on the entire surface of one side of the sheet-like support (4a). Then, if necessary, apply a loss-of-adhesive adhesive that can form an adhesive insulating layer (2a) to the laminate obtained by drying and curing, and the entire surface of the release treatment surface of the active energy permeable separator (1a). It can also be obtained by laminating a laminate obtained by processing and drying as necessary.
As the separator (1), instead of the active energy ray-permeable separator (1a), a separator (1b) having no active energy ray permeability may be used to obtain the same pressure-sensitive adhesive sheet as in FIG. 1 [1]. it can.

Next, as a first method, as shown in FIG. 1 [2], an active energy ray non-transmissive portion and an active energy ray transmissive portion are provided on the active energy ray permeable separator (1a) of the laminated sheet (10). The pattern-forming mask (5) is overlapped, and the adhesive insulating layer (2a) is partially irradiated with active energy rays through the separator (1a) and the pattern-forming mask (5). A partially tacky insulating layer (2b) having a pattern composed of a cured portion that has been cured and has lost its tackiness and an uncured portion that has tackiness is formed.
Alternatively, as a second method, as shown in FIG. 1 [2 ′], the pattern forming mask (5) is overlaid on the active energy ray-permeable sheet-like support (4 a) of the laminated sheet (10). The adhesive insulating layer (2a) is partially irradiated with active energy rays through the support (4a) and the pattern forming mask (5), the irradiated portion is cured, and the cured portion has lost its adhesiveness. A partially adhesive insulating layer (2b) having a pattern composed of an uncured part having adhesiveness is formed.
This method is preferably used when the separator (1) is a separator (1b) having no active energy ray permeability.
Alternatively, as a third method, when the surface of the pattern forming mask (5) is peeled, the separator (1) is peeled from the laminated sheet as shown in FIG. The exposed surface of the adhesive insulating layer (2a) is overlaid with the surface of the pattern forming mask (5) that has been peeled off, and the adhesive layer (2a) is partially covered with the pattern forming mask (5). Are irradiated with active energy rays, and the irradiated part is cured to form a partially adhesive insulating layer (2b) having a pattern comprising a cured part that has lost its adhesiveness and an uncured part that has adhesiveness.
After forming the partially adhesive insulating layer (2b), in the case of the first and second methods, by peeling off the separator (1a) or the separator (1b) and the pattern forming mask (5), or In the case of the third method, by removing the pattern-forming mask (5), the cured part having lost adhesiveness on the sheet-like support (4a) as shown in FIG. A partial pressure-sensitive adhesive sheet in which a partial pressure-sensitive adhesive layer (2b) having a pattern consisting of 2b-2) and an uncured part (2b-1) having adhesiveness is laminated can be obtained.

And as shown to FIG. 1 [4], electroconductive powder (6) is made to contact the surface of a partial adhesive sheet, and as shown to FIG. 1 [5], the uncured part (2b-1) which has adhesiveness The conductive powder (6) on the cured part (2b-2) that has lost its adhesiveness is removed while the conductive powder (6) is attached to the surface.
Next, as shown in FIG. 1 [6], the entire surface of the active energy ray-permeable sheet-like support (4a) is irradiated with active energy rays, thereby causing the adhesiveness in the partially adhesive insulating layer (2b). The uncured part (2b-1) having a solid is cured, the conductive powder (6) adhering to the surface is fixed, and the active energy ray-permeable sheet-like support as shown in FIG. 1 [7] (4a), the insulating layer (2c) cured by active energy ray irradiation provided on the entire surface of one surface of the sheet-like support (4a), and partially provided on the insulating layer (2c). A conductive pattern sheet comprising the conductive pattern (7) is obtained.
In addition, before irradiating the active energy ray to the whole surface from the active energy ray-permeable sheet-like support (4a) side, the pressure is applied in advance, and conductive powder ( Part of 6) can also be pushed in.

  FIG. 1 shows a case in which active energy rays are partially irradiated to the adhesive insulating layer (2a) using a pattern formation mask (5) having an active energy ray non-transmissive portion and an active energy ray transmissive portion. However, a conductive pattern can also be formed by irradiating an active energy ray controlled to a desired irradiation pattern without using such a pattern formation mask (5).

  In the present invention, as shown in FIG. 2, metal plating is further performed on each conductive pattern (7) in the conductive pattern sheet shown in [7] of FIG. 1, and conductive powder and metal plating layer (8) are applied. A conductive pattern (9) consisting of

  In the present invention, the mask for pattern formation (5) having an active energy ray non-transmission part and an active energy ray transmission part used when partially irradiating an active energy ray is widely used in the production of a printing plate. In addition to the silver salt type that is used, a stainless steel plate with a desired pattern (hole) drawn by a laser and the formed hole as a light transmission part can also be used.

Examples of the conductive powder (6) used in the present invention include gold, silver, copper, platinum, palladium, rhodium, osmium, ruthenium, iridium, iron, tin, zinc, cobalt, nickel, chromium, titanium, tantalum, A powder made of a metal selected from the group consisting of tungsten and indium, or an alloy thereof, having an average particle diameter of 0.001 to 20.0 μm is preferable.
Only one type of conductive powder (6) may be used, or two or more types may be used in combination.

  By providing metal plating layer (8) by further performing metal plating on the conductive pattern formed of conductive powder, the resistance value of the conductive pattern can be further stabilized. Examples of the metal plating method include electrolytic plating and electroless plating.

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
The weight average molecular weight and number average molecular weight of the resins described in the examples are the weight average molecular weight and number average molecular weight in terms of polystyrene determined by GPC measurement, and the conditions for GPC measurement are as follows. .
Equipment: Shodex GPC System-21 (manufactured by Showa Denko)
Column: Shodex KF-802, KF-803L, KF-805L
A total of 3 (made by Showa Denko) are connected and used.
Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Temperature: 40 ° C
Sample concentration: 0.3% by weight
Sample injection volume: 100 μl

[Synthesis of polyurethane polyurea resin]
[Synthesis Example 1]
A number average molecular weight (hereinafter referred to as “Mn”) obtained from adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. ) = 1006 diol 414 parts, dimethylol butanoic acid 8 parts, isophorone diisocyanate 145 parts, and toluene 40 parts were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, in a mixture of 27 parts of isophoronediamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, 816 parts of the urethane prepolymer solution obtained above was added, at 70 ° C. The mixture was reacted for 3 hours to obtain a polyurethane polyurea resin solution having a weight average molecular weight (hereinafter referred to as “Mw”) = 54,000. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane polyurea resin solution having a solid content of 30%.

[Synthesis of polyester resin]
[Synthesis Example 2]
In a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and reflux dehydrator, dimethyl terephthalate 184.4 parts, neopentyl glycol 94.8 parts, ethylene glycol 94.2 parts, 2-methyl-1,3 -Charge 54.7 parts of propanediol and 0.035 parts of zinc acetate. When the raw material can be heated and melted and stirred, stirring is started and the temperature is gradually increased from 170 ° C. to 220 ° C. over 3 hours while removing distilled methanol out of the system at normal pressure. Hold for 1 hour. The internal temperature is once cooled to 170 ° C., 92.6 parts of adipic acid, 65.8 parts of isophthalic acid, and 113.6 parts of 1,4-cyclohexanedicarboxylic acid are added, and the distilled water is removed from the system under normal pressure. However, the temperature was raised to 240 ° C. over 3 hours, and the reaction was continued at 240 ° C. until the acid value reached 15 mgKOH / g.
Next, the device was changed to a vacuum decompression device, 0.06 part of tetrabutyl titanate was added, and the reaction was continued for 6 hours under a reduced pressure of 2 Torr at a temperature of 240 ° C., and then placed in a Teflon (registered trademark) container. I took it out.
The number average molecular weight of this resin was 18000, and the glass transition temperature was 27 ° C.
Subsequently, the obtained polyester resin was taken in a 100-part flask, and 100 parts of toluene was added and dissolved. Next, 10 parts of ethylene glycol bistrimellitate dianhydride was added to the flask and reacted at a temperature of 100 ° C. for 5 hours to obtain a solution of a polyester resin having a carboxyl group. The acid value of the resin was 30 mg KOH / g, the number average molecular weight was 22000, and the glass transition temperature was 28 ° C.

(Example 1)
Acrylic polymer having carboxyl group as viscoelastic polymer: 100 parts by weight, aromatic isocyanate curing agent: 3 parts by weight as curing agent for viscoelastic polymer, polyfunctional urethane acrylate: 50 parts by weight, radical photopolymerization initiator: 5 parts by weight, polymerization inhibitor: 0.05 parts by weight, blended in a weight ratio of 5 parts by weight of ethyl acetate as a diluent solvent to obtain an adhesive for forming an adhesive insulating layer, and the surface of the PET film is peeled off The separator thus obtained was coated on the release-treated surface to obtain an adhesive insulating layer (2a) having a thickness of 20 μm.
Separately, 100 parts by weight of the polyurethane polyurea resin solution obtained in Synthesis Example 1 in terms of solid content, epoxy resin (manufactured by Adeka: “EP4100”): 25 parts by weight, imidazole compound (manufactured by Shikoku Kasei: “2E4MZ”): A resin composition for forming an anchor coat layer is obtained by blending at a weight ratio of 5 parts by weight, and the thickness of the anchor coat layer after drying is placed on a PET film ("Embret S50" manufactured by Unitika). The anchor coat layer (3) was formed by coating and drying to a thickness of 10 μm.
Next, the adhesive insulating layer (2a) and the anchor coat layer (3) are bonded so that the surface is in contact with the separator (1), and the adhesive insulating layer can lose its adhesiveness after being cured by irradiation with active energy rays. A laminated sheet in which (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a) were sequentially laminated was produced.

  Next, on the separator (1) of the laminated sheet obtained above, a photomask in which a stripe pattern with a width of 50 μm is formed at a pitch of 100 μm is pasted and irradiated with 1000 mJ of ultraviolet light from the mask side, thereby partially sticking insulation Layer (2b) was formed.

  After UV irradiation, the photomask is removed, the separator (1) is peeled off, copper powder with an average particle size of 5 μm is sprayed onto the exposed surface of the partially adhesive insulating layer (2b), and a stripe pattern with a line width of 50 μm is conductive. Pattern (7) was obtained.

  After forming the conductive pattern, ultraviolet rays were irradiated from the active energy ray transmitting sheet-like support (4a) side to cure the uncured portion of the partially adhesive insulating layer (2b), thereby obtaining a conductive pattern sheet.

(Example 2)
The polyurethane polyurea resin solution obtained in Synthesis Example 1 is 100 parts by weight in solid content, epoxy resin (manufactured by Adeka: “EP4100”): 20 parts by weight, imidazole compound (manufactured by Shikoku Kasei: “2E4MZ”): 5 weights The resin composition for forming an anchor coat layer was obtained by blending at a weight ratio of parts, and this was applied to a PEN film (“Teonex Q81” manufactured by Teijin DuPont), and the thickness of the anchor coat layer after drying was 10 μm. The anchor coat layer (3) was formed by coating and drying.
Then, separately, the adhesive insulating layer (2a) surface obtained in the same manner as in Example 1 and the anchor coat layer (3) surface were bonded so that they were in contact with each other. A laminated sheet in which the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a), which can lose their properties, are sequentially laminated, and A conductive pattern sheet was obtained in the same procedure.

(Example 3)
100 parts by weight of the polyester resin solution obtained in Synthesis Example 2 in solid content, epoxy resin (manufactured by Adeka: “EP4100”): 15 parts by weight, imidazole compound (manufactured by Shikoku Kasei: “2E4MZ”): 2.5 A resin composition for forming an anchor coat layer was obtained by blending at a weight ratio of parts by weight, and this was dried on a polyimide film (“Kapton 200H” manufactured by Toray DuPont), and the thickness of the anchor coat layer after drying was 10 μm. Coating and drying were performed to form an anchor coat layer (3).
Then, separately, the adhesive insulating layer (2a) surface obtained in the same manner as in Example 1 and the anchor coat layer (3) surface were bonded so that they were in contact with each other. A laminated sheet was produced in which the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a) that can lose their properties were laminated sequentially.
Thereafter, when the uncured portion of the formed partially adhesive insulating layer (2b) is cured, the conductive energy is changed in the same manner as in Example 1 except that an electron beam is used instead of ultraviolet rays as the active energy ray. Sex pattern sheet was obtained.

Example 4
100 parts by weight of the polyester resin solution obtained in Synthesis Example 2, epoxy resin (manufactured by Adeka: “EP4100”): 10 parts by weight, imidazole compound (manufactured by Shikoku Kasei: “2E4MZ”): 2.5 A resin composition for forming an anchor coat layer is obtained by blending at a weight ratio of parts by weight, and this is applied to the corona-treated surface of an aramid film (“Aramica” manufactured by Teijin Advanced Films) and the anchor coat layer after drying The anchor coat layer (3) was formed by coating and drying so as to have a thickness of 10 μm.
Then, separately, the adhesive insulating layer (2a) surface obtained in the same manner as in Example 1 and the anchor coat layer (3) surface were bonded so that they were in contact with each other. A laminated sheet was produced in which the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a) that can lose their properties were laminated sequentially.
Thereafter, when the uncured portion of the formed partially adhesive insulating layer (2b) is cured, the conductive energy is changed in the same manner as in Example 1 except that an electron beam is used instead of ultraviolet rays as the active energy ray. Sex pattern sheet was obtained.

(Comparative Example 1)
100 parts by weight of an acrylic resin solution (manufactured by Toyo Ink Manufacturing Co., Ltd .: “BPS5977”) and 0.5 parts by weight of solid curing agent of an isocyanate-based curing agent (manufactured by Toyo Ink Manufacturing Co., Ltd .: “BHS8515”). A resin composition for forming an anchor coat layer is obtained by blending at a weight ratio, and this is placed on a PEN film (“Teonex Q81” manufactured by Teijin DuPont) so that the thickness of the anchor coat layer after drying is 10 μm. The anchor coat layer was formed by coating and drying.
Subsequently, the adhesive insulating layer (2a) surface obtained in the same manner as in Example 1 and the anchor coat layer surface were bonded so that the adhesive layer was lost after curing by irradiation with the separator (1) and active energy rays. A laminated sheet obtained by sequentially laminating an adhesive insulating layer (2a) to be obtained, an anchor coat layer, and an active energy ray-permeable sheet-like support (4a) is prepared, and further a conductive pattern is obtained in the same procedure as in Example 1. A sheet was obtained.

(Comparative Example 2)
Urethane resin solution (manufactured by Sanyo Chemical Co., Ltd .: “Samprene IB465”) is blended at a weight ratio of 100 parts by weight in solid content and epoxy resin (manufactured by ADEKA: “EP4100”): 20 parts by weight to form an anchor coat layer. Resin composition for coating, and this is coated on a polyimide film (“Kapton 200H” manufactured by Toray DuPont) so that the thickness of the anchor coat layer after drying is 10 μm, and the anchor coat layer is formed by drying. did.
Subsequently, the adhesive insulating layer (2a) surface obtained in the same manner as in Example 1 and the anchor coat layer surface were bonded so that the adhesive layer was lost after curing by irradiation with the separator (1) and active energy rays. A laminated sheet was produced in which the resulting adhesive insulating layer (2a), anchor coat layer, and active energy ray-permeable sheet-like support (4a) were sequentially laminated.
Thereafter, when the uncured portion of the formed partially adhesive insulating layer (2b) is cured, the conductive energy is changed in the same manner as in Example 1 except that an electron beam is used instead of ultraviolet rays as the active energy ray. Sex pattern sheet was obtained.

(Comparative Example 3)
A polyester resin solution (Toyobo Co., Ltd .: “Byron GK140” dissolved in an organic solvent) is blended at a weight ratio of 100 parts by weight in solid content and epoxy resin (“EP4100” from Adeka): 10 parts by weight. A resin composition for forming an anchor coat layer is obtained, and this is coated on a polyimide film (“Kapton 200H” manufactured by Toray DuPont) so that the thickness of the anchor coat layer after drying is 10 μm. Thus, an anchor coat layer was formed.
Subsequently, the adhesive insulating layer (2a) surface obtained in the same manner as in Example 1 and the anchor coat layer surface were bonded so that the adhesive layer was lost after curing by irradiation with the separator (1) and active energy rays. A laminated sheet was produced in which the resulting adhesive insulating layer (2a), anchor coat layer (3), and active energy ray-permeable sheet-like support (4a) were sequentially laminated.
Thereafter, when the uncured portion of the formed partially adhesive insulating layer (2b) is cured, the conductive energy is changed in the same manner as in Example 1 except that an electron beam is used instead of ultraviolet rays as the active energy ray. Sex pattern sheet was obtained.

  For the conductive pattern sheets obtained in the examples and comparative examples, the adhesion between the anchor coat layer and the support, the adhesion between the insulating layer having no tackiness and the anchor coat layer, and the heat resistance are as follows. evaluated. The results are shown in Table 1.

[Adhesiveness]
About the electroconductive pattern sheet obtained by the Example and the comparative example, the adhesive tape ("31B tape" made by Nitto Denko Corporation) is pasted on the electroconductive pattern surface by reciprocating 2kg rubber roll in an atmosphere of 23 ° C and relative humidity of 50%. Then, a 180 ° peel test was conducted between the adhesive tape and the support at a pulling speed of 10 m / min, and the peeled surface was confirmed and evaluated.
If the adhesiveness is insufficient, the pressure-sensitive adhesive tape is peeled off at the interface between the support and the anchor coat layer or at the interface between the anchor coat layer and the insulating layer while being stuck on the insulating layer.
○: No peeling at each interface of the support, anchor coat layer and insulating layer ×: There is peeling at the interface between the support and anchor coat layer or the anchor coat layer and insulating layer

[Heat-resistant]
About the electroconductive pattern sheet obtained by the Example and the comparative example, it heat-processed for 60 seconds with 260 degreeC electric oven. The state of the anchor coat layer after the heat treatment was visually observed, and the presence or absence of appearance defects such as foaming, floating and peeling was evaluated.
Each test was conducted 5 times, and the number of appearance defects was evaluated.
○: Appearance failure did not occur △: Appearance failure occurred within 2 times ×: Appearance failure occurred 3 times or more

It is typical sectional drawing which shows the one aspect | mode of the manufacturing method of the electroconductive pattern sheet of this invention. It is typical sectional drawing which shows another aspect of the manufacturing method of the electroconductive pattern sheet of this invention.

Explanation of symbols

1: Separator 1a: Active energy ray transmissive separator 2a: Adhesive insulating layer 2b: Partially adhesive insulating layer 2b-1: Adhesive uncured portion 2b-2: Adhesive loss cured portion 2c: Cured insulating layer
3: Anchor coat layer
4a: Active energy ray-permeable sheet-like support
5: Mask for pattern formation having active energy ray transmission part and non-transmission part 6: Conductive powder 7: Conductive pattern 8: Metal plating layer 9: Conductive pattern 10 consisting of conductive powder and metal plating layer: Laminate sheet 11: Conductive pattern sheet 12: Conductive pattern sheet 13 having a metal-plated conductive pattern: Irradiation of active energy rays

Claims (6)

The separator (1), the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a), which can lose the adhesiveness after being cured by active energy ray irradiation, are sequentially provided. A laminated sheet that is laminated,
The anchor coat layer (3)
Urethane prepolymer having an isocyanate group at the end, obtained by reacting a diol compound (a) having a carboxyl group, a polyol (b) other than (a) and an organic diisocyanate (c) having a number average molecular weight of 500 to 8000. A polyurethane polyurea resin (A) obtained by reacting (d) with a polyamino compound (e), and
A laminated sheet characterized by being formed from a resin composition (I) containing an epoxy resin (B) having two or more epoxy groups. The separator (1), the adhesive insulating layer (2a), the anchor coat layer (3), and the active energy ray-permeable sheet-like support (4a), which can lose the adhesiveness after being cured by active energy ray irradiation, are sequentially provided. A laminated sheet that is laminated,
The anchor coat layer (3)
A polyester resin (c4) having a hydroxyl group obtained by reacting the diol (c1) with a dibasic acid or dibasic acid anhydride (c2) or a dialkyl ester (c3) of a dibasic acid, and three in the molecule A polyester resin (C) obtained by reacting the above polybasic acid having a carboxyl group or its anhydride (c5), and
A laminated sheet characterized by being formed from a resin composition (II) containing an epoxy resin (D) having two or more epoxy groups.   The laminated sheet according to claim 1 or 2, wherein the separator (1) is an active energy ray permeable separator (1a). From the active energy ray-permeable separator (1a) side of the laminated sheet according to claim 3, the adhesive insulating layer (2a) is irradiated with active energy rays in a pattern,
After forming a partially adhesive insulating layer (2b) having a pattern consisting of a cured part that has lost adhesiveness and an uncured part that has adhesiveness,
Removing the active energy ray permeable separator (1a);
The conductive powder (6) is brought into contact with the exposed surface of the partially adhesive insulating layer (2b), and the conductive powder (6) is applied to the uncured portion having adhesiveness in the partially adhesive insulating layer (2b). Remove the conductive powder (6) that is attached and in contact with the cured part that has lost its adhesiveness,
Next, the active energy ray-transmitting sheet-like support (4a) side of the laminated sheet is irradiated with active energy rays to cure the uncured portion of the partial adhesive insulating layer (2b) and to have no adhesiveness. While forming the layer (2c)
Fix the conductive powder (6) adhering to the uncured part to the insulating layer (2c),
A method for producing a conductive pattern sheet, comprising forming a conductive pattern (7) of conductive powder (6) on an insulating layer (2c).   5. The method for producing a conductive pattern sheet according to claim 4, wherein metal plating is further performed on the conductive pattern (7).   The electroconductive pattern sheet obtained by the manufacturing method of Claim 4 or 5.

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