Low-dielectric resin composition, adhesion imparting agent, low-dielectric adhesive composition, low-dielectric adhesive molded article, low-dielectric adhesive, and laminate

Abstract

The low dielectric resin composition includes a polyolefin resin. The polyolefin resin contains a styrene elastomer (A) and a cyclic olefin polymer (B) having an alicyclic ring in the main chain. The content ratio of the styrene-based elastomer (A) is 30 parts by mass or more and 89 parts by mass or less relative to 100 parts by mass of the total of the styrene-based elastomer (A) and the cyclic olefin-based polymer (B).

Description

Technical Field

[0001] The present invention relates to a low dielectric resin composition, an adhesion imparting agent, a low dielectric adhesive composition, a low dielectric adhesive molded product, a low dielectric adhesive and a laminate. Background Art

[0002] The wired circuit board includes, for example, a resin layer (insulating layer) containing a thermosetting resin and a conductor layer containing a metal. The wired circuit board is widely used in various industrial fields.

[0003] In recent years, in a wired circuit board, it is required to directly bond a resin layer (insulating layer) to a conductor layer. Therefore, it is proposed to add an adhesion-imparting agent to the resin layer (insulating layer) to impart adhesion to the resin layer (insulating layer).

[0004] As the adhesion imparting agent, for example, a resin having high adhesion and low dielectric constant can be used. As such a resin, for example, the following low dielectric constant resin is proposed. The low dielectric constant resin comprises a maleic anhydride grafted modified resin. As the maleic anhydride grafted modified resin, a maleic anhydride grafted (styrene-ethylene-butylene-styrene) block copolymer is used alone, or a maleic anhydride grafted cyclic olefin copolymer is used alone (for example, see Patent Document 2 (Example 1 and Example 4).).

[0005] Furthermore, in a wired circuit board, it is also required that the resin layer (insulating layer) and the conductor layer be bonded together using an interlayer adhesive instead of being directly bonded together.

[0006] As an interlayer adhesive, a resin having, for example, high adhesion and low dielectric constant can also be used. For example, the following resin is proposed. That is, the resin comprises a mixture of a maleic acid-modified propylene·1-butene copolymer and a maleic acid-modified styrene-ethylene-propylene-styrene copolymer. More specifically, the above-mentioned resin is manufactured by modifying a mixture of a propylene·1-butene copolymer and a styrene-ethylene-propylene-styrene copolymer with maleic acid (for example, see Patent Document 1 (Manufacturing Example 5 and Example 1).).

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2018-154823

[0010] Patent Document 2: Japanese Patent Application Publication No. 2022-043966 Summary of the invention

[0011] Problems to be solved by the invention

[0012] On the other hand, tackifiers and interlayer adhesives are required to have more excellent heat resistance.

[0013] In addition, the tackifier is mixed with the thermosetting resin to form a resin layer (insulating layer). Therefore, the tackifier is required to have improved affinity (compatibility) with the thermosetting resin.

[0014] Furthermore, the interlayer adhesive is required to have excellent adhesion to the resin layer (insulating layer). Therefore, the interlayer adhesive is also required to have improved affinity (adhesion) with the thermosetting resin.

[0015] The present invention provides a low dielectric resin composition, an adhesion imparting agent, a low dielectric adhesive composition, a low dielectric adhesive molded product, a low dielectric adhesive and a laminate, which have excellent adhesion and low dielectric properties, excellent heat resistance, and excellent affinity with thermosetting resins.

[0016] Means for solving problems

[0017] The present invention [1] includes a low dielectric resin composition, which is a low dielectric resin composition containing a polyolefin resin, wherein the polyolefin resin contains a styrene elastomer (A) and a cyclic olefin polymer (B) having an alicyclic ring in the main chain, and the content ratio of the styrene elastomer (A) is 30 parts by mass or more and 89 parts by mass or less relative to 100 parts by mass of the total amount of the styrene elastomer (A) and the cyclic olefin polymer (B).

[0018] The present invention [2] comprises the low dielectric resin composition described in [1] above, wherein the weight average molecular weight of the styrene elastomer (A) is 70,000 to 110,000.

[0019] The present invention [3] comprises the low dielectric resin composition described in [1] or [2] above, wherein the aforementioned styrene-based elastomer (A) contains a structural unit derived from styrene, and the content ratio of the aforementioned structural unit derived from styrene is 10% by mass or more and 40% by mass or less relative to the total amount of the aforementioned styrene-based elastomer (A).

[0020] The present invention [4] includes the low dielectric resin composition according to any one of [1] to [3] above, wherein the styrene-based elastomer (A) does not contain a structural unit derived from butene.

[0021] The present invention [5] comprises the low dielectric resin composition according to any one of [1] to [4] above, wherein the cyclic olefin polymer (B) has a glass transition temperature of 100° C. to 140° C.

[0022] The present invention [6] includes the low dielectric resin composition according to any one of [1] to [5] above, wherein the polyolefin-based resin is modified with a functional group-containing monomer.

[0023] The present invention [7] includes the low dielectric resin composition described in [6] above, wherein the functional group-containing monomer includes a carboxyl group-containing monomer.

[0024] The present invention [8] includes an adhesion-imparting agent comprising the low dielectric resin composition according to any one of the above [1] to [7].

[0025] The present invention [9] includes a low dielectric adhesive composition comprising a thermosetting resin and the adhesion-imparting agent described in the above [8], wherein the thermosetting resin comprises at least one selected from the group consisting of epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin having unsaturated double bonds and liquid crystal polymer.

[0026] The present invention

[10] includes a low-dielectric adhesive molded product comprising a cured product of the low-dielectric adhesive composition described in [9] above.

[0027] The present invention

[11] includes a laminate comprising: an insulating layer comprising the low-dielectric adhesive molded product described in

[10] above; and a conductive layer disposed on at least one surface of the insulating layer.

[0028] The present invention

[12] includes a low dielectric adhesive comprising the low dielectric resin composition according to any one of [1] to [7] above.

[0029] The present invention

[13] includes a laminate comprising: an insulating layer; a conductive layer arranged opposite to the insulating layer; and an adhesive layer arranged between the insulating layer and the conductive layer and bonding the insulating layer and the conductive layer, wherein the adhesive layer comprises the low dielectric adhesive described in

[12] above.

[0030] The present invention

[14] includes a laminate comprising: a first conductor layer; a second conductor layer arranged opposite to the first conductor layer; and an adhesive layer arranged between the first conductor layer and the second conductor layer and bonding the first conductor layer and the second conductor layer, wherein the adhesive layer comprises the low dielectric adhesive described in

[12] above.

[0031] Effects of the Invention

[0032] Low dielectric resin composition of the present invention contains polyolefin resin as resin component. And, polyolefin resin contains styrene elastomer (A) and cyclic olefin polymer (B) with alicyclic ring on main chain with specific ratio. Therefore, low dielectric resin composition has excellent adhesiveness and low dielectric property, also has excellent heat resistance, and has excellent affinity (compatibility, adhesion) with thermosetting resin.

[0033] The adhesive imparting agent, low dielectric adhesive composition and low dielectric adhesive molding of the present invention comprise the above-mentioned low dielectric resin composition. Therefore, the adhesive imparting agent, low dielectric adhesive composition and low dielectric adhesive molding have excellent adhesion and low dielectricity, also have excellent heat resistance, and have excellent affinity (compatibility, adhesion) with thermosetting resin.

[0034] The laminate of the present invention has an insulating layer. The insulating layer includes the above-mentioned low dielectric adhesive molding. Therefore, in the laminate, the insulating layer has excellent adhesion and low dielectric properties, also has excellent heat resistance, and has excellent affinity (compatibility, adhesion) with thermosetting resin.

[0035] The low dielectric adhesive of the present invention comprises the low dielectric resin composition described above, and therefore has excellent adhesion and low dielectric properties, excellent heat resistance, and excellent affinity (compatibility and adhesion) with thermosetting resins.

[0036] In addition, the laminate of the present invention has an adhesive layer. The adhesive layer contains the above-mentioned low dielectric adhesive. Therefore, in the laminate, the adhesive layer has excellent adhesion and low dielectric properties, also has excellent heat resistance, and has excellent affinity (compatibility, adhesion) with thermosetting resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] [ Figure 1 ] Figure 1 It is a schematic diagram showing a copper-clad laminate as a first embodiment of a laminate.

[0038] [ Figure 2 ] Figure 2 It is a schematic diagram showing a circuit board according to a second embodiment of the laminate.

[0039] [ Figure 3 ] Figure 3 It is a schematic diagram showing a copper-clad laminate as a third embodiment of a laminate.

[0040] [ Figure 4 ] Figure 4 It is a schematic diagram showing a circuit board according to a fourth embodiment of the laminate.

[0041] [ Figure 5 ] Figure 5 A shows a process diagram for manufacturing a circuit board as a fifth embodiment of a laminate, and a process for preparing a copper foil with a carrier. Figure 5 B shows the process of forming the first resist layer, Figure 5 C shows a step of forming the first conductor layer.

[0042] [ Figure 6 ] Figure 6 D Figure 5 Next, a process diagram for manufacturing a circuit board is shown, in which a process of removing the first resist layer is shown. Figure 6 E shows the process of removing the copper foil exposed from the first conductor layer. Figure 6 F shows the process of laminating the adhesive layer. Figure 6 G shows a step of laminating the copper foil with a carrier on the adhesive layer.

[0043] [ Figure 7 ] Figure 7 H Figure 6 Next, a process diagram for manufacturing a circuit board is shown, in which a carrier layer is peeled off. Figure 7 I shows the process of forming a through hole, Figure 7 J shows the process of forming the filled hole, Figure 7 K shows a step of forming a second resist layer.

[0044] [ Figure 8 ] Figure 8 L Figure 7 Next, a process diagram for manufacturing a circuit board is shown, in which a second conductor layer is formed. Figure 8 M shows the process of removing the second resist layer, Figure 8 N represents a step of removing the copper foil exposed from the second conductor layer. Figure 8 O shows the process of peeling off the carrier layer. DETAILED DESCRIPTION

[0045] 1. Low dielectric resin composition

[0046] The low dielectric resin composition is, for example, a resin composition contained in an insulating layer (described later) or an adhesive layer (described later) in a laminated body described later. The low dielectric resin composition contains a polyolefin-based resin.

[0047] The polyolefin-based resin contains a styrene-based elastomer (A) and a cyclic olefin-based polymer (B) having an alicyclic ring in its main chain.

[0048] (1) Styrene elastomer

[0049] Examples of the styrene-based elastomer (A) include copolymers of styrene and chain olefins.

[0050] Examples of the chain olefin include chain olefins having 2 to 8 carbon atoms. Examples of the chain olefins having 2 to 8 carbon atoms include ethylene, propylene, butene, pentene, hexene, octene, and 3-methyl-1-pentene. These can be used alone or in combination of two or more. Preferred chain olefins include ethylene used alone, propylene used alone, and ethylene and propylene used in combination.

[0051] As the chain olefin, more preferably, ethylene and propylene are used in combination.

[0052] The styrene-based elastomer (A) can be produced by a known method. For example, styrene and a linear olefin are polymerized in the presence of a known initiator (e.g., an alkyl lithium compound). Thus, the styrene-based elastomer (A) can be obtained. It should be noted that the polymerization conditions can be appropriately set according to the purpose and use.

[0053] The styrene-based elastomer (A) contains a structural unit derived from styrene and a structural unit derived from a chain olefin. Preferably, the styrene-based elastomer (A) is composed of a structural unit derived from styrene and a structural unit derived from a chain olefin.

[0054] From the viewpoint of affinity with thermosetting resin, the content of the structural unit derived from styrene is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, relative to the total amount of styrene elastomer (A). In addition, from the viewpoint of low dielectricity, the content of the structural unit derived from styrene is, for example, 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less, relative to the total amount of styrene elastomer (A).

[0055] In addition, from the viewpoint of low dielectric properties, the content of the structural unit derived from the chain olefin is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, relative to the total amount of the styrene-based elastomer (A). In addition, from the viewpoint of affinity with the thermosetting resin, the content of the structural unit derived from the chain olefin is, for example, 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less, relative to the total amount of the styrene-based elastomer (A).

[0056] It should be noted that the content ratio of the structural unit derived from styrene and the content ratio of the structural unit derived from chain olefin can be calculated based on the formula of the polymerization raw material of the styrene-based elastomer (A). More specifically, the content ratio of the structural unit derived from styrene can be calculated as the ratio of styrene relative to the total amount of the polymerization raw material (styrene and chain olefin). In addition, the content ratio of the structural unit derived from chain olefin can be calculated as the ratio of chain olefin relative to the total amount of the polymerization raw material (styrene and chain olefin).

[0057] The styrene-based elastomer (A) preferably contains a structural unit derived from ethylene as a structural unit derived from a chain olefin. The content ratio of the structural unit derived from ethylene can be appropriately set depending on the purpose and application.

[0058] In addition, the styrene-based elastomer (A) preferably contains a structural unit derived from propylene as a structural unit derived from a chain olefin. In addition, the content ratio of the structural unit derived from propylene can be appropriately set according to the purpose and application.

[0059] The styrene-based elastomer (A) may contain a structural unit derived from butene as a structural unit derived from a chain olefin as necessary. The content ratio of the structural unit derived from butene can be appropriately set according to the purpose and application.

[0060] On the other hand, when the content ratio of the structural unit derived from styrene in the styrene-based elastomer (A) is low, the content ratio of the structural unit derived from butene is preferably low from the viewpoint of affinity with the thermosetting resin.

[0061] In other words, when the styrene-based elastomer (A) contains a structural unit derived from butene, it is preferred to set the content ratio of the structural unit derived from styrene to be high.

[0062] From the viewpoint of affinity with the thermosetting resin, when the styrene-based elastomer (A) contains a structural unit derived from butene, the content ratio of the structural unit derived from styrene is, for example, 10% by mass or more, preferably 20% by mass or more, and particularly preferably 25% by mass or more, relative to the total amount of the styrene-based elastomer (A). In addition, the content ratio of the structural unit derived from styrene is preferably 90% by mass or less, more preferably 85% by mass or less, relative to the total amount of the styrene-based elastomer (A).

[0063] It is particularly preferred that the styrene-based elastomer (A) does not contain a structural unit derived from butene. More specifically, when the content ratio of the structural unit derived from styrene in the styrene-based elastomer (A) is less than 25% by mass, it is preferred that the styrene-based elastomer (A) does not contain a structural unit derived from butene as a structural unit derived from a chain olefin.

[0064] In other words, when the content ratio of the structural unit derived from styrene in the styrene-based elastomer (A) is high (for example, 25% by mass or more), the styrene-based elastomer (A) may contain a structural unit derived from butene. In addition, when the content ratio of the structural unit derived from styrene is high, the styrene-based elastomer (A) may not contain a structural unit derived from butene.

[0065] From the viewpoint of affinity with the thermosetting resin, it is particularly preferred that the styrene-based elastomer (A) contains structural units derived from styrene at a ratio of 25% by mass or more and contains no structural units derived from butene; or, contains structural units derived from styrene at a ratio of 25% by mass or more and contains structural units derived from butene; or, contains structural units derived from styrene at a ratio of less than 25% by mass and contains no structural units derived from butene.

[0066] As styrene elastomer (A), more specifically, for example, styrene-ethylene-propylene copolymer (SEP), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-isobutylene-styrene copolymer (SIBS) can be mentioned. In addition, as copolymer, for example, random copolymer and block copolymer (hereinafter the same) can be mentioned. They can be used alone or in combination of two or more.

[0067] From the viewpoint of affinity with thermosetting resins, preferred styrene-based elastomers (A) include styrene-ethylene-propylene copolymers (SEP), styrene-ethylene-propylene-styrene copolymers (SEPS), styrene-butadiene-styrene copolymers (SBS), and styrene-ethylene-butylene-styrene copolymers (SEBS).

[0068] From the viewpoint of heat resistance, low dielectric properties, and affinity with thermosetting resins, more preferred examples of the styrene-based elastomer (A) include styrene-ethylene-propylene-styrene copolymers (SEPS) and styrene-ethylene-butylene-styrene copolymers (SEBS).

[0069] From the viewpoint of heat resistance, low dielectric properties, and affinity with thermosetting resins, the styrene-based elastomer (A) is preferably a styrene-based elastomer (A) that does not contain a structural unit derived from butene, and more specifically, a styrene-ethylene-propylene-styrene copolymer (SEPS).

[0070] In addition, from the viewpoints of heat resistance, low dielectric properties, and affinity with thermosetting resins, as the styrene-based elastomer (A), a styrene-based elastomer (A) containing a structural unit derived from butene and containing a relatively large amount of structural units derived from styrene is further preferably mentioned. In such a case, as described above, the content ratio of the structural unit derived from butene relative to the total amount of the styrene-based elastomer (A) is preferably 20% by mass or more, and particularly preferably 25% by mass or more.

[0071] That is, as the styrene-based elastomer (A), more preferably there are styrene-based elastomers (A) containing no structural unit derived from butene and styrene-based elastomers (A) containing structural units derived from butene and 25% by mass or more of structural units derived from styrene.

[0072] In addition, from the viewpoints of heat resistance, low dielectric properties, and affinity with thermosetting resins, particularly preferred are styrene-based elastomers (A) containing no structural unit derived from butene, and more specifically, styrene-ethylene-propylene-styrene copolymers (SEPS).

[0073] From the viewpoint of low dielectricity, the weight average molecular weight of the styrene elastomer (A) is, for example, 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, further preferably 70,000 or more, and particularly preferably 90,000 or more. In addition, from the viewpoint of low dielectricity and the stability of the diluent (varnish) described later, the weight average molecular weight of the styrene elastomer (A) is, for example, 500,000 or less, preferably 300,000 or less, more preferably 200,000 or less, further preferably 110,000 or less, and particularly preferably 100,000 or less.

[0074] In addition, the weight average molecular weight of the styrene-based elastomer (A) can be measured as a molecular weight in terms of standard polystyrene by gel permeation chromatography.

[0075] The styrene-based elastomer (A) may be used alone or in combination of two or more. In addition, a commercially available product may be used as the styrene-based elastomer (A).

[0076] Examples of commercially available products of the styrene-based elastomer (A) include trade name SEPTON series (manufactured by KURARAY), trade name Kraton series (manufactured by Kraton Polymer Japan Corporation), and trade name Tuftec series (manufactured by Asahi Kasei).

[0077] (2) Cyclic olefin polymers

[0078] Examples of the cyclic olefin polymer (B) having an alicyclic ring in the main chain include polymers of cyclic olefins and hydrogenated products thereof.

[0079] Examples of cyclic olefins include cyclic hydrocarbon compounds containing an ethylenically unsaturated bond. Examples of cyclic hydrocarbon compounds include cyclic hydrocarbon compounds having 6 to 30 carbon atoms. More specifically, examples of cyclic olefins include bicyclo[2.2.1]-hept-2-ene (also known as norbornene) and its derivatives, tricyclo[4.3.0.1 2.5 ]-3-decene and its derivatives, tricyclo[4.4.0.1 2.5 ]-3-decene and its derivatives, tetracyclo[4.4.0.1 2.5 .1 7.10 ]-3-dodecene and its derivatives, pentacyclic [6.5.1.1 3.6 .0 2.7 .0 9.13 ]-4-pentadecaene and its derivatives, hexacyclo[6.6.1.1 3.6 .1 10.13 .0 2.7 .0 9.14 ]-4-heptadecene and its derivatives, and heptacyclic [8.7.0.1 2.9 .1 4.7 .1 11.17 .0 3.8 .0 12.16 ]-5-eicosene and its derivatives. These may be used alone or in combination of two or more. Preferably, bicyclo[2.2.1]-hept-2-ene (also known as norbornene) is mentioned.

[0080] The polymer of cyclic olefin can be produced by known methods. For example, a cyclic olefin can be subjected to ring-opening metathesis polymerization by known methods. Thus, a ring-opening metathesis polymer of cyclic olefin can be obtained. It should be noted that the polymerization conditions can be appropriately set according to the purpose and use.

[0081] Furthermore, if necessary, the ring-opening metathesis polymer of cyclic olefin may be hydrogenated by a known method, thereby obtaining a hydrogenated product of the ring-opening metathesis polymer of cyclic olefin.

[0082] The cyclic olefin polymer and its hydrogenated product may be used alone or in combination of two or more.

[0083] Examples of the cyclic olefin polymer (B) having an alicyclic ring in the main chain include copolymers of cyclic olefins and chain olefins (cyclic olefin copolymers), and hydrogenated products thereof.

[0084] Examples of the cyclic olefin include the above-mentioned cyclic hydrocarbon compounds, and preferably tetracyclo[4.4.0.1 2.5 .1 7.10 ]-3-dodecene and its derivatives, more preferably tetracyclo[4.4.0.1 2.5 .1 7.10 ]-3-dodecene.

[0085] Examples of the chain olefin include the above-mentioned chain olefins having 2 to 8 carbon atoms, and preferably ethylene is used.

[0086] The copolymer of chain olefin and cyclic olefin can be manufactured by known methods. For example, in the presence of known catalysts (for example, vanadium catalysts, aluminum catalysts and metallocene catalysts), chain olefin and cyclic olefin are polymerized. Thus, a copolymer of chain olefin and cyclic olefin can be obtained. It should be noted that the polymerization conditions can be suitably set according to the purpose and use.

[0087] Furthermore, if necessary, the copolymer of chain olefin and cyclic olefin may be hydrogenated by a known method, thereby obtaining a hydrogenated product of the copolymer of chain olefin and cyclic olefin.

[0088] The copolymer of a linear olefin and a cyclic olefin and its hydrogenated product may be used alone or in combination of two or more.

[0089] As the cyclic olefin polymer (B), preferably a copolymer of a chain olefin and a cyclic olefin can be mentioned. In other words, the cyclic olefin polymer (B) preferably contains a structural unit derived from a chain olefin and a structural unit derived from a cyclic olefin. More preferably, the cyclic olefin polymer (B) is composed of a structural unit derived from a chain olefin and a structural unit derived from a cyclic olefin.

[0090] It should be noted that the proportion of the structural unit from chain olefins and the proportion of the structural unit from cyclic olefins can be appropriately set according to the purpose and use. For example, in order to adjust the weight average molecular weight and glass transition temperature of the cyclic olefin polymer (B), the proportion of the structural unit from chain olefins and the proportion of the structural unit from cyclic olefins can be appropriately set.

[0091] From the viewpoint of heat resistance, the weight average molecular weight of the cyclic olefin polymer (B) is, for example, 10,000 or more, preferably 50,000 or more, more preferably 80,000 or more, further preferably 100,000 or more, and particularly preferably 112,000 or more. In addition, the weight average molecular weight of the cyclic olefin polymer (B) is, for example, 500,000 or less, preferably 300,000 or less, more preferably 200,000 or less, further preferably 150,000 or less, and particularly preferably 118,000 or less.

[0092] In addition, the weight average molecular weight of a cyclic olefin type polymer (B) can be measured as a molecular weight converted into standard polystyrene by gel permeation chromatography.

[0093] From the viewpoint of heat resistance, the glass transition temperature of the cyclic olefin polymer (B) is, for example, 60° C. or higher, preferably 70° C. or higher, more preferably 80° C. or higher, further preferably 90° C. or higher, and particularly preferably 100° C. or higher. In addition, from the viewpoint of the stability of the dilution liquid (varnish) described later and the affinity (compatibility) with the thermosetting resin, the glass transition temperature of the cyclic olefin polymer (B) is, for example, 200° C. or lower, preferably 175° C. or lower, more preferably 150° C. or lower, further preferably 140° C. or lower, further preferably 130° C. or lower, further preferably 120° C. or lower, and particularly preferably 110° C. or lower.

[0094] In addition, the glass transition temperature of the cyclic olefin polymer (B) can be measured according to JIS K 7122 (2012).

[0095] The cyclic olefin polymer (B) may be used alone or in combination of two or more. In addition, a commercially available product may be used as the cyclic olefin polymer (B).

[0096] Commercially available products of the cyclic olefin polymer (B) include, for example, the product name ZEONEX series (hydrogenated products of cyclic monomer polymers, manufactured by Zeon of Japan), the product name ZEONOR series (hydrogenated products of cyclic monomer polymers, manufactured by Zeon of Japan), and the product name APEL series (copolymers of chain olefins and cyclic olefins, manufactured by Mitsui Chemicals).

[0097] (3) Proportion

[0098] The polyolefin resin can be obtained by mixing the above-mentioned styrene elastomer (A) and the above-mentioned cyclic olefin polymer (B) using a known method. Preferably, the polyolefin resin can be obtained by melt-kneading the styrene elastomer (A) and the above-mentioned cyclic olefin polymer (B) in a twin-screw extruder.

[0099] Then, in the polyolefin resin, the blending ratio of the styrene elastomer (A) and the cyclic olefin polymer (B) is adjusted to fall within a specific range.

[0100] More specifically, from the viewpoint of affinity with the thermosetting resin, the content of the styrene elastomer (A) is 30 parts by mass or more, preferably 35 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 45 parts by mass or more, based on 100 parts by mass of the total amount of the styrene elastomer (A) and the cyclic olefin polymer (B). In addition, from the viewpoint of heat resistance, the content of the styrene elastomer (A) is 89 parts by mass or less, preferably 85 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the styrene elastomer (A) and the cyclic olefin polymer (B).

[0101] That is, from the viewpoint of heat resistance, the content of the cyclic olefin polymer (B) is 11 parts by mass or more, preferably 15 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more, relative to 100 parts by mass of the total amount of the styrene elastomer (A) and the cyclic olefin polymer (B). In addition, from the viewpoint of affinity with the thermosetting resin, the content of the cyclic olefin polymer (B) is 70 parts by mass or less, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less, relative to 100 parts by mass of the total amount of the styrene elastomer (A) and the cyclic olefin polymer (B).

[0102] If the polyolefin resin contains a styrene elastomer (A) and a cyclic olefin polymer (B) having an alicyclic ring in the main chain in the above-mentioned specific proportion, the low dielectric resin composition has excellent adhesion and low dielectric properties, excellent heat resistance, and excellent affinity (compatibility, adhesion) with thermosetting resins.

[0103] In addition, the content ratio of the cyclic olefin polymer (B) relative to 100 parts by mass of the styrene-based elastomer (A) is, for example, 12 parts by mass or more, preferably 25 parts by mass or more, and more preferably 50 parts by mass or more. In addition, the content ratio of the cyclic olefin polymer (B) relative to 100 parts by mass of the styrene-based elastomer (A) is, for example, 235 parts by mass or less, preferably 185 parts by mass or less, and more preferably 150 parts by mass or less.

[0104] When the ratio of the styrene elastomer (A) to the cyclic olefin polymer (B) is within the above range, the low dielectric resin composition has excellent adhesion and low dielectric properties, excellent heat resistance, and excellent affinity (compatibility, adhesion) with thermosetting resins.

[0105] (4) Other olefin polymers

[0106] The polyolefin resin may contain other olefin polymers (C) as necessary. Other olefin polymers (C) are known olefin polymers other than the styrene elastomer (A) and the cyclic olefin polymer (B).

[0107] As other olefin polymers (C), for example, polyethylene, polypropylene, polyisobutylene, poly-1-butene, poly-4-methylpentene, ethylene·propylene copolymer, propylene·butene copolymer, ethylene·butene copolymer, ethylene·4-methyl-1-pentene copolymer, propylene·4-methyl-1-pentene copolymer, butene·4-methyl-1-pentene copolymer, ethylene·hexene copolymer, and ethylene·vinyl acetate copolymer can be enumerated. They can be used alone or in combination of two or more. In addition, the content ratio of other olefin polymers can be suitably set within the range of not hindering the excellent effect of the present invention.

[0108] The content ratio of other olefin polymers (C) relative to the total amount of the polyolefin resin is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 0% by mass. That is, the polyolefin resin preferably does not contain other olefin polymers (C). In other words, the polyolefin resin is preferably composed of a styrene elastomer (A) and a cyclic olefin polymer (B).

[0109] (5) Modified polyolefin resin

[0110] The polyolefin-based resin may be an unmodified polyolefin-based resin or a modified polyolefin-based resin.

[0111] The unmodified polyolefin resin is a polyolefin resin comprising a styrene elastomer (A) and a cyclic olefin polymer (B) and not modified by a modifier (described later). The modified polyolefin resin is a polyolefin resin comprising a styrene elastomer (A) and a cyclic olefin polymer (B) and modified by a modifier (described later). From the viewpoint of adhesion with a metal (e.g., a conductor layer described later), the polyolefin resin preferably includes a modified polyolefin resin.

[0112] The modified polyolefin-based resin can be obtained, for example, by modifying a polyolefin-based resin with a known modifying agent.

[0113] As the modifier, for example, a functional group-containing monomer can be cited. As the functional group-containing monomer, for example, a carboxyl group-containing monomer, a sulfonyl group-containing monomer, an amino group-containing monomer, a hydroxyl group-containing monomer, a glycidyl group-containing monomer, and a halogen-containing monomer can be cited. They can be used alone or in combination of two or more. From the viewpoint of adhesion with a metal (for example, a conductor layer described later), as the functional group-containing monomer, a carboxyl group-containing monomer can be preferably cited.

[0114] As the carboxyl group-containing monomer, for example, unsaturated acids can be mentioned. As unsaturated acids, for example, maleic acid, fumaric acid, itaconic acid and (meth) acrylic acid can be mentioned. In addition, as unsaturated acids, their anhydrides can also be mentioned. They can be used alone or in combination of two or more. As the carboxyl group-containing monomer, preferably maleic acid and its anhydride can be mentioned, and more preferably maleic anhydride can be mentioned.

[0115] That is, as modified polyolefin resin, for example, acid-modified polyolefin resin can be cited. As acid-modified polyolefin resin, for example, maleic acid (anhydride) modified polyolefin resin, fumaric acid (anhydride) modified polyolefin resin, itaconic acid (anhydride) modified polyolefin resin and (meth) acrylic acid modified polyolefin resin can be cited. They can be used alone or in combination of two or more. As modified polyolefin resin, preferably maleic anhydride modified polyolefin resin can be cited.

[0116] The method for obtaining the modified polyolefin resin is not particularly limited. For example, a known method is used to react an unmodified polyolefin resin with a modifier. For example, a modifier is added when the styrene elastomer (A) and the cyclic olefin polymer (B) are mixed. In addition, for example, before the above-mentioned mixing, a modifier is added to the styrene elastomer (A) and / or the cyclic olefin polymer (B), so that the styrene elastomer (A) and / or the cyclic olefin polymer (B) react with the modifier. Preferably, a modifier is added when the styrene elastomer (A) and the cyclic olefin polymer (B) are mixed.

[0117] The addition amount of the modifier can be suitably set according to the purpose and use. For example, when using a carboxyl group-containing monomer as a modifier, relative to 100 parts by mass of the total amount of styrene elastomer (A) and cyclic olefin polymer (B), the carboxyl group-containing monomer is, for example, more than 0.1 parts by mass, preferably more than 0.5 parts by mass. In addition, relative to 100 parts by mass of the total amount of styrene elastomer (A) and cyclic olefin polymer (B), the carboxyl group-containing monomer is, for example, less than 20 parts by mass, preferably less than 10 parts by mass, more preferably less than 5 parts by mass.

[0118] In addition, when using a carboxyl group-containing monomer as a modifier, a modified initiator is mixed as required. As the modified initiator, for example, known grafting catalysts can be mentioned, and more specifically, known peroxides and known azo compounds can be mentioned. The mixing ratio of the modified initiator can be appropriately set according to the purpose and use.

[0119] Then, the styrene elastomer (A) and the cyclic olefin polymer (B) are mixed with a modifier and reacted to obtain a modified polyolefin resin. The reaction conditions are not particularly limited and can be appropriately set according to the type and amount of the modifier.

[0120] Such a modified polyolefin resin contains a styrene elastomer (A) modified by a modifier (modified styrene elastomer) and a cyclic olefin polymer (B) modified by a modifier (modified cyclic olefin polymer). The modified polyolefin resin can improve the adhesion with metal (for example, the conductor layer described later).

[0121] When a carboxyl group-containing monomer is used as a modifier, the acid value of the modified polyolefin resin is, for example, 0.1 mgKOH / g or more, preferably 0.5 mgKOH / g or more. In addition, the acid value of the modified polyolefin resin is, for example, 100 mgKOH / g or less, preferably 60 mgKOH / g or less. It should be noted that the acid value can be measured in accordance with JIS K 2501 (2003).

[0122] (6) Non-polyolefin resin

[0123] In the low dielectric resin composition, the resin component may contain a non-polyolefin resin in addition to the above-mentioned polyolefin resin. The non-polyolefin resin is a known resin other than the polyolefin resin. As the non-polyolefin resin, for example, a (meth) acrylic resin may be cited. They may be used alone or in combination of two or more.

[0124] From the viewpoint of affinity with the thermosetting resin, in the low dielectric resin composition, the resin component preferably does not contain a non-polyolefin resin. That is, in the low dielectric resin composition, the resin component preferably consists of the above-mentioned polyolefin resin.

[0125] (7) Organic solvents

[0126] The low dielectric resin composition can be diluted with an organic solvent. More specifically, the low dielectric resin composition can be dissolved and / or dispersed in an organic solvent. That is, a dilution (solution and / or dispersion) of the low dielectric resin composition can be prepared.

[0127] The solid content concentration of the diluent (solution and / or dispersion) of the low dielectric resin composition is, for example, more than 5% by mass, preferably more than 10% by mass. In addition, the solid content concentration of the diluent (solution and / or dispersion) of the low dielectric resin composition is, for example, less than 50% by mass, preferably less than 30% by mass.

[0128] (8) Additives

[0129] The low dielectric resin composition and / or its diluent can contain known additives. As additives, for example, plasticizers, defoamers, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retardants, antioxidants, ultraviolet light absorbers, anti-hydrolysis agents, weathering stabilizers, heat stabilizers, dyes, inorganic pigments, organic pigments, curing agents, crosslinking agents, thermal initiators (thermal free radical polymerization initiators), silane coupling agents, release agents, inorganic particles and organic particles can be enumerated. They can be used alone or in combination with more than two kinds. The addition ratio and the time of addition of the additive can be suitably set according to the purpose and use.

[0130] (9) Effects

[0131] The above-mentioned low dielectric resin composition contains polyolefin resin as resin component. And, polyolefin resin contains styrene elastomer (A) and cyclic olefin polymer (B) with alicyclic ring on main chain with specific ratio. Therefore, the low dielectric resin composition has excellent adhesiveness and low dielectric property, also has excellent heat resistance, and has excellent affinity (compatibility, adhesion) with thermosetting resin.

[0132] The relative dielectric constant (measurement condition: 10 GHz) of the low dielectric resin composition (solid content) is, for example, 1.5 or more, preferably 1.9 or more. In addition, the relative dielectric constant (measurement condition: 10 GHz) of the low dielectric resin composition (solid content) is, for example, 3.0 or less, preferably 2.5 or less.

[0133] It should be noted that the relative dielectric constant can be measured according to the examples described below (the same applies below).

[0134] The dielectric loss tangent (measurement condition: 10 GHz) of the low dielectric adhesive composition (solid component) is, for example, 0.0001 or more, preferably 0.0003 or more. In addition, the dielectric loss tangent (measurement condition: 10 GHz) of the low dielectric adhesive composition (solid component) is, for example, 0.004 or less, preferably 0.002 or less. It should be noted that the relative dielectric constant can be measured according to the embodiments described below.

[0135] Such a low dielectric resin composition can be suitably used as an adhesion-imparting agent and / or a low dielectric adhesive in the production of a laminate.

[0136] 2. Laminated body

[0137] The laminate is a circuit substrate or a circuit substrate material. The circuit substrate is, for example, a laminate having a conductor layer (circuit layer) having a circuit pattern. The circuit substrate material is a laminate that can be processed into a circuit substrate. More specifically, the circuit substrate material is, for example, a laminate having a conductor layer (non-circuit layer) without a circuit pattern and capable of forming a circuit pattern by processing. As a circuit substrate material, for example, a copper-clad laminate can be cited.

[0138] The laminate can be produced by using the low dielectric resin composition. Hereinafter, a method for producing a circuit board or a circuit board material as a laminate using the low dielectric resin composition will be described in detail.

[0139] (1) First Embodiment

[0140] Figure 1 It is a schematic cross-sectional view showing a copper-clad laminate according to a first embodiment as a laminate. In the first embodiment, the above-mentioned low dielectric resin composition is used as an adhesion-imparting agent.

[0141] More specifically, Figure 1 In the embodiment, a copper-clad laminate 1 includes an insulating layer 2 having adhesiveness (hereinafter referred to as an adhesive insulating layer) and a conductive layer 4 disposed on at least one surface of the adhesive insulating layer 2 .

[0142] The adhesive insulating layer 2 includes a resin molded product having low dielectric properties and adhesive properties (hereinafter referred to as a low dielectric adhesive molded product). The adhesive insulating layer 2 is preferably composed of the low dielectric adhesive molded product, or composed of an impregnated base material and a low dielectric adhesive molded product.

[0143] The low-dielectric adhesive molded product is, for example, a molded and cured product of the following low-dielectric adhesive composition (molding material).

[0144] The low-dielectric adhesive composition (molding material) contains, for example, a thermosetting resin (uncured thermosetting resin) and an adhesion-imparting agent (additive).

[0145] As the thermosetting resin, for example, epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin and liquid crystal polymer with unsaturated double bonds can be mentioned. They can be used alone or in combination of two or more. As the thermosetting resin, preferably polyphenylene ether resin can be mentioned.

[0146] In other words, the thermosetting resin includes at least one selected from the group consisting of epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin having unsaturated double bonds and liquid crystal polymer. The thermosetting resin preferably includes polyphenylene ether resin. The thermosetting resin is preferably composed of polyphenylene ether resin.

[0147] The adhesion-imparting agent (additive) contains the above-mentioned low-dielectric resin composition, and preferably consists of the above-mentioned low-dielectric resin composition.

[0148] The low-dielectric adhesive composition (molding material) can be prepared by, for example, mixing a thermosetting resin and an adhesion-imparting agent by a known method.

[0149] The mixing ratio of the thermosetting resin and the adhesion imparting agent is not particularly limited. The adhesion imparting agent is, for example, 1 part by mass or more, preferably 5 parts by mass or more, relative to 100 parts by mass of the thermosetting resin. In addition, the adhesion imparting agent is, for example, 400 parts by mass or less, preferably 150 parts by mass or less, relative to 100 parts by mass of the thermosetting resin.

[0150] The thermosetting resin is, for example, 20% by mass or more, preferably 40% by mass or more, relative to the total amount of the thermosetting resin and the adhesion-imparting agent. In addition, the thermosetting resin is, for example, 99% by mass or less, preferably 95% by mass or less, relative to the total amount of the thermosetting resin and the adhesion-imparting agent.

[0151] In addition, relative to the total amount of the thermosetting resin and the adhesion-imparting agent, the adhesion-imparting agent is, for example, 1% by mass or more, preferably 5% by mass or more. In addition, relative to the total amount of the thermosetting resin and the adhesion-imparting agent, the adhesion-imparting agent is, for example, 80% by mass or less, preferably 60% by mass or less.

[0152] In addition, low dielectric adhesive composition (molding material) can also include additives except thermosetting resin and bonding agent.As additive, for example, plasticizer, defoamer, leveling agent, mildew inhibitor, rust inhibitor, matting agent, flame retardant, thixotropic agent, tackifier, thickener, lubricant, antistatic agent, surfactant, reaction retarder, antioxidant, ultraviolet absorber, anti-hydrolysis agent, weathering stabilizer, heat stabilizer, dye, inorganic pigment, organic pigment, curing agent, crosslinking agent, thermal initiator (thermal free radical polymerization initiator), silane coupling agent, release agent, inorganic particles and organic particles can be enumerated.They can be used alone or in combination with more than 2 kinds.The addition ratio and the time of addition of additive can be suitably set according to purpose and use.

[0153] From the viewpoint of thermosetting, the low dielectric adhesive composition (molding material) preferably contains a thermal initiator. As a thermal initiator, for example, an organic peroxide can be mentioned. As an organic peroxide, for example, diisopropyl peroxide, 1- (2- tert-butyl peroxide isopropyl) -1-isopropylbenzene, 1- (2- tert-butyl peroxide isopropyl) -3-isopropylbenzene, 1,3-bis (tert-butyl peroxide isopropyl) benzene, 2,5- dimethyl -2.5- bis (tert-butyl peroxide) hexane and 2,5- dimethyl -2,5- (tert-butyl peroxide) -hex-3-yne can be mentioned. They can be used alone or in combination with more than two kinds.

[0154] For example, relative to the total amount of 100 parts by mass of the resin component of the bonding agent (low dielectric resin composition), the addition amount of the thermal initiator is, for example, more than 0.1 parts by mass, preferably more than 1.0 parts by mass. In addition, for example, relative to the total amount of 100 parts by mass of the resin component of the bonding agent (low dielectric resin composition), the addition amount of the thermal initiator is, for example, less than 10 parts by mass, preferably less than 5 parts by mass.

[0155] For example, when the adhesive insulating layer 2 is composed of a low-dielectric adhesive molded product, the adhesive insulating layer 2 can be formed by molding and curing a low-dielectric adhesive composition (molding material) by a known method.

[0156] For example, a low dielectric adhesive composition (molding material) is applied to a known substrate (e.g., a copper plate and a release liner) and dried as required. Thus, a coating of the low dielectric adhesive composition (molding material) is obtained. Then, the coating is cured (thermosetting) by heating.

[0157] Thereby, a low-dielectric adhesive molded product (adhesive insulating layer 2) composed of a cured product of the low-dielectric adhesive composition (molding material) can be obtained.

[0158] For example, when the adhesive insulating layer 2 is composed of an impregnation base material and a low-dielectric adhesive molded product, the adhesive insulating layer 2 can be formed by impregnating the impregnation base material with a low-dielectric adhesive composition (molding material) and drying and curing the impregnation base material.

[0159] For example, a low dielectric adhesive composition (molding material) is impregnated into a glass cloth as an impregnation substrate, dried as required, and then the glass cloth and the low dielectric adhesive composition (molding material) impregnated into the glass cloth are cured (thermosetting) by heating.

[0160] Thereby, a low-dielectric adhesive molded product (adhesive insulating layer 2 ) including the glass cloth and a cured product of the low-dielectric adhesive composition (molding material) can be obtained.

[0161] In addition, the shape and size of the low-dielectric adhesive molded product (adhesive insulating layer 2) can be appropriately set according to the purpose and application.

[0162] The conductor layer 4 is a thin film formed of a known conductive material. As the conductive material, copper can be cited, for example. The conductor layer 4 can be formed by a known film forming method. The thickness of the conductor layer 4 can be adjusted to be thinner, for example. Thus, a circuit pattern can be formed by a subtractive method. The thickness of the conductor layer 4 is, for example, 50 μm or less.

[0163] The conductor layer 4 is disposed on at least one surface of the adhesive insulating layer 2. The conductor layer 4 is preferably disposed on both surfaces of the adhesive insulating layer 2. Figure 1 In the embodiment, the conductor layer 4 is arranged on both surfaces of the adhesive insulating layer 2 .

[0164] More specifically, the conductor layer 4 is formed by a known method so as to be in contact with the surface of the adhesive insulating layer 2. Thus, the conductor layer 4 is bonded to the adhesive insulating layer 2. As a result, the copper-clad laminate 1 including the adhesive insulating layer 2 and the conductor layer 4 is obtained.

[0165] It should be noted that the method for obtaining the copper-clad laminate 1 is not limited to the above method. For example, first prepare a conductor layer 4 formed by a metal foil. Then, a low dielectric adhesive composition (molding material) is applied to the conductor layer 4 and dried as required. Then, the low dielectric adhesive composition (molding material) is thermally cured. Thus, an adhesive insulating layer 2 can be formed on the surface of the conductor layer 4. As a result, a copper-clad laminate 1 having an adhesive insulating layer 2 and a conductor layer 4 in contact with the surface of the adhesive insulating layer 2 can be obtained.

[0166] The copper-clad laminate 1 has an insulating layer 2. The insulating layer 2 includes the low dielectric adhesive molding. Therefore, in the copper-clad laminate 1, the insulating layer 2 has excellent adhesion and low dielectric properties, excellent heat resistance, and excellent affinity (compatibility, adhesion) with thermosetting resins, and therefore has excellent strength.

[0167] In addition, the above-mentioned adhesion imparting agent (additive), low dielectric adhesive composition (molding material) and low dielectric adhesive molding (adhesive insulating layer 2) comprise the above-mentioned low dielectric resin composition. Therefore, adhesion imparting agent (additive), low dielectric adhesive composition (molding material) and low dielectric adhesive molding (adhesive insulating layer 2) have excellent adhesion and low dielectricity, also have excellent heat resistance, and have excellent affinity (compatibility) with thermosetting resin, therefore, have excellent strength.

[0168] (2) Second Embodiment

[0169] Figure 2It is a schematic cross-sectional view showing a circuit board of the second embodiment as a laminate. In the second embodiment, similarly to the first embodiment, the above-mentioned low dielectric resin composition is used as an adhesion-imparting agent.

[0170] More specifically, the copper-clad laminate 1 of the first embodiment described above can be processed to form the circuit substrate 11. That is, the conductor layer 4 of the copper-clad laminate 1 can be etched by a known method to form the circuit 14. As a result, Figure 2 As shown in FIG. 1 , a circuit board 11 according to the second embodiment is formed as a laminate.

[0171] In such a circuit substrate 11, the adhesive insulating layer 2 includes a low dielectric adhesive molding. Therefore, in the circuit substrate 11, the adhesive insulating layer 2 has excellent adhesion and low dielectric properties, excellent heat resistance, and excellent affinity (compatibility, adhesion) with thermosetting resin, and therefore has excellent strength.

[0172] (3) Third Embodiment

[0173] Figure 3 It is a schematic cross-sectional view showing a copper-clad laminate according to a third embodiment of the laminate. In the third embodiment, the above-mentioned low-dielectric resin composition is used as a low-dielectric adhesive.

[0174] Figure 3 In the embodiment, the copper-clad laminate 21 includes: an insulating layer 22; a conductor layer 24 disposed opposite to the insulating layer 22; and an adhesive layer 23 disposed between the insulating layer 22 and the conductor layer 24 and bonding the insulating layer 22 and the conductor layer 24. In the copper-clad laminate 21, the adhesive layer 23 is formed of the above-mentioned low dielectric adhesive.

[0175] The insulating layer 22 is, for example, an insulating layer having no adhesiveness (a non-adhesive insulating layer). The insulating layer 22 contains, for example, the aforementioned thermosetting resin. The insulating layer 22 is preferably composed of the aforementioned thermosetting resin.

[0176] Similar to the above-mentioned conductor layer 4, the conductor layer 24 is a thin film formed of a known conductive material. As the conductive material, copper can be cited, for example. The conductor layer 24 can be formed by a known film forming method. The thickness of the conductor layer 24 can be adjusted to be thinner, for example. Thus, the circuit pattern can be formed by a subtractive method. The thickness of the conductor layer 24 is, for example, 50 μm or less.

[0177] The adhesive layer 23 is interposed between the insulating layer 22 and the conductive layer 24. The adhesive layer 23 is a dried product of a low dielectric adhesive. The low dielectric adhesive includes, for example, the above-mentioned low dielectric resin composition.

[0178] The low dielectric adhesive is preferably a diluted solution of the above-mentioned low dielectric resin composition.

[0179] In the case of manufacturing the copper-clad laminate 21, for example, first prepare the insulating layer 22 and the conductor layer 24. Then, a low-dielectric adhesive is applied to one side of the insulating layer 22. Then, the conductor layer 24 is bonded to one side of the low-dielectric adhesive, and the low-dielectric adhesive is dried. Thus, the copper-clad laminate 21 can be obtained. It should be noted that the copper-clad laminate 21 can also be manufactured in the reverse order of the above. That is, in this method, a low-dielectric adhesive is applied to one side of the conductor layer 24. Then, the insulating layer 22 is bonded to one side of the low-dielectric adhesive, and the low-dielectric adhesive is dried. Thus, the copper-clad laminate 21 can be obtained.

[0180] In the above-mentioned copper-clad laminate 21, the insulating layer 22 and the conductor layer 24 are bonded using an adhesive layer 23 (low dielectric adhesive). That is, the copper-clad laminate 21 has an adhesive layer 23. And, the adhesive layer 23 (low dielectric adhesive) comprises the above-mentioned low dielectric resin composition. Therefore, in the copper-clad laminate 21, the adhesive layer 23 (low dielectric adhesive) has excellent adhesion and low dielectricity, also has excellent heat resistance, and has excellent affinity (adhesion) with thermosetting resin.

[0181] It should be noted that, in the copper-clad laminate 21 of the third embodiment described above, the adhesive layer 23 and the conductor layer 24 are formed only on one side of the insulating layer 22, but the adhesive layer 23 and the conductor layer 24 may be formed on both sides of the insulating layer 22. In addition, in such a case, the copper-clad laminate 21 may not have the insulating layer 22. That is, the conductor layer 24 may be formed on both sides of the adhesive layer 23. In other words, the two conductor layers 24 may be bonded together using the adhesive layer 23. In such a case, the adhesive layer 23 is also used as the insulating layer 22.

[0182] (4) Fourth Embodiment

[0183] Figure 4 It is a schematic cross-sectional view showing a circuit board of the fourth embodiment as a laminate. In the fourth embodiment, similarly to the third embodiment, the above-mentioned low dielectric resin composition is used as a low dielectric adhesive.

[0184] More specifically, the copper-clad laminate 21 of the third embodiment described above can be processed to form the circuit substrate 31. More specifically, the conductor layer 24 of the copper-clad laminate 21 can be etched by a known method to form the circuit 34. As a result, Figure 4 As shown in FIG. 1 , a circuit board 31 according to the fourth embodiment is formed as a laminate.

[0185] In such a circuit board, the insulating layer 22 and the circuit 34 formed of a conductor layer are bonded together by the adhesive layer 23 .

[0186] In such a circuit substrate 31, the insulating layer 22 and the circuit 34 formed by the conductor layer are bonded by the bonding layer 23 (low dielectric adhesive). The bonding layer 23 (low dielectric adhesive) comprises the above-mentioned low dielectric resin composition. Therefore, in the circuit substrate 31, the bonding layer 23 (low dielectric adhesive) has excellent adhesion and low dielectricity, also has excellent heat resistance, and has excellent affinity (adhesion) with thermosetting resin.

[0187] It should be noted that, in the circuit substrate 31 of the fourth embodiment described above, the adhesive layer 23 and the circuit 34 are formed only on one side of the insulating layer 22, but the adhesive layer 23 and the circuit 34 may be formed on both sides of the insulating layer 22. In addition, in such a case, the circuit substrate 31 may not have the insulating layer 22. That is, the circuit 34 may be formed on both sides of the adhesive layer 23. In other words, the two circuits 34 may be bonded together using the adhesive layer 23. In such a case, the adhesive layer 23 is also used as the insulating layer 22.

[0188] (5) Fifth Embodiment

[0189] Figures 5 to 8 It is a cross-sectional view of the process for manufacturing the circuit board of the fifth embodiment as a laminate. In the fifth embodiment, the above-mentioned low dielectric resin composition is used as a low dielectric adhesive.

[0190] Figures 5 to 8 In the embodiment, the circuit substrate 41 is a multilayer circuit substrate having at least two conductor layers. More specifically, the circuit substrate 41 can be seen in Figure 8 O, comprising: a first conductor layer 40; a second conductor layer 50 disposed opposite to the first conductor layer 40; and an adhesive layer 51 disposed between the first conductor layer 40 and the second conductor layer 50 and bonding the first conductor layer 40 and the second conductor layer 50. In addition, in the circuit board 41, the adhesive layer 51 is formed of the above-mentioned low dielectric adhesive (preferably a diluted solution of a low dielectric resin composition).

[0191] In order to manufacture such a circuit substrate 41, first, Figure 5 As shown in A, a copper foil 42 with a carrier is prepared. The copper foil 42 with a carrier includes a carrier layer 43 and a copper foil 44 laminated on one side of the carrier layer 43 .

[0192] The carrier layer 43 is not particularly limited, and a known release sheet can be cited. The copper foil 44 can be laminated on the carrier layer 43 using a known method. The thickness of the copper foil 44 can be appropriately set according to the purpose and use. In addition, the copper foil 44 can be surface treated as needed. As a surface treatment, for example, a roughening treatment can be cited.

[0193] Then, in this method, if Figure 5 As shown in FIG. 2B , a first resist layer 45 of a predetermined shape is formed on one surface of the copper foil 44. The first resist layer 45 can be formed, for example, by applying a known resist solution and performing exposure and development. Alternatively, the first resist layer 45 can be formed by exposing and etching a dry film resist.

[0194] Then, in this method, if Figure 5 C, the first plating layer 46 is formed. The first plating layer 46 can be formed, for example, by electrolytic plating. In the electrolytic plating method, for example, the carrier layer 43, the copper foil 44, and the first resist layer 45 are immersed in an electrolytic plating solution, and then power is supplied to the copper foil 44. As a result, the first plating layer 46 is formed on the surface of one side of the copper foil 44 with a reverse pattern of the first resist layer 45. That is, the first plating layer 46 has a circuit pattern.

[0195] Then, in this method, if Figure 6 As shown in D, the first resist layer 45 is removed by a known method. Next, in this method, Figure 6 As shown in FIG. E, the copper foil 44 exposed from the first plating layer 46 is removed by a known method. Thus, the first conductor layer 40 including the copper foil 44 remaining without being removed and the first plating layer 46 laminated on the copper foil 44 can be formed. That is, the first conductor layer 40 includes the copper foil 44 and the first plating layer 46. The first conductor layer 40 is preferably composed of the copper foil 44 and the first plating layer 46.

[0196] Then, in this method, if Figure 6 As shown in F, an adhesive layer 51 formed of a low dielectric adhesive is laminated on the carrier layer 43 , the first plating layer 46 , and the copper foil 44 .

[0197] More specifically, in this method, for example, a cast film of a low dielectric adhesive is prepared. Next, the cast film is pressed against the carrier layer 43, the first plating layer 46, and the copper foil 44. Thus, the cast film covers the first plating layer 46 and the copper foil 44. In addition, the cast film forms the adhesive layer 51.

[0198] On the other hand, in this method, a copper foil 52 with a carrier is prepared separately. The copper foil 52 with a carrier includes a carrier layer 53 and a copper foil 54 laminated on the other side of the carrier layer 53. Then, in this method, as Figure 6 As shown in G, the copper foil 54 of the copper foil with a carrier 52 is laminated on the adhesive layer 51 .

[0199] Then, in this method, if Figure 7 As shown in H, the carrier layer 53 of the copper foil 52 with a carrier is peeled off. Next, in this method, as Figure 7As shown in FIG. 1, the copper foil 54 and the adhesive layer 51 are opened by a known method to form a through hole 58. In addition, the first plating layer 46 is exposed from the through hole 58. Next, in this method, as shown in FIG. Figure 7 As shown in J, the through hole 58 is filled with a conductive material to form a filled hole 59. It should be noted that as an example of the conductive material, copper can be cited.

[0200] Then, in this method, if Figure 7 As shown in FIG. 1 , a second resist layer 55 of a predetermined shape is formed on one surface of the copper foil 54. The second resist layer 55 can be formed, for example, by applying a known resist solution and performing exposure and development. In addition, the second resist layer 55 can also be formed by a dry film resist in the same manner as the first resist layer 45.

[0201] Then, in this method, if Figure 8 As shown in FIG. 1 , the second plating layer 56 is formed. The second plating layer 56 can be formed, for example, by electrolytic plating. Thus, the second plating layer 56 is formed on one surface of the copper foil 54 in a reverse pattern of the second resist layer 55. That is, the second plating layer 56 has a circuit pattern.

[0202] Then, in this method, if Figure 8 As shown in FIG. 4, the second resist layer 55 is removed by a known method. Next, in this method, Figure 8 As shown in FIG. 1 , the copper foil 54 exposed from the second plating layer 56 is removed by a known method. Thus, the second conductor layer 50 including the copper foil 54 remaining without being removed and the first plating layer 56 laminated on the copper foil 54 can be formed. That is, the second conductor layer 50 includes the copper foil 54 and the second plating layer 56. The second conductor layer 50 is preferably composed of the copper foil 54 and the second plating layer 56.

[0203] Then, in this method, if Figure 8 As shown in FIG. 0 , the carrier layer 43 is peeled off. Thus, the copper foil 44 is exposed. As a result, the circuit board 1 is formed.

[0204] Moreover, in the above-mentioned circuit substrate 41, the first conductor layer 40 and the second conductor layer 50 are bonded by an adhesive layer 51 (low dielectric adhesive). That is, the circuit substrate 41 has an adhesive layer 51. Moreover, the adhesive layer 51 (low dielectric adhesive) comprises the above-mentioned low dielectric resin composition. Therefore, in the circuit substrate 41, the adhesive layer 51 (low dielectric adhesive) has excellent adhesion and low dielectric properties, and also has excellent heat resistance.

[0205] Example

[0206] Next, the present invention is described based on embodiments and comparative examples, but the present invention is not limited thereto. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass. In addition, the specific numerical values ​​of the mixing ratio (containing ratio), physical property values, parameters, etc. used in the following description can be replaced by the upper limit value (numerical value defined in the form of "below", "less than") or the lower limit value (numerical value defined in the form of "above", "greater than") of the corresponding mixing ratio (containing ratio), physical property values, parameters, etc. recorded in the above-mentioned "specific implementation method".

[0207] 1. Preparation of raw materials

[0208] Preparation Example 1-1 (Styrene Elastomer)

[0209] As shown in Tables 1 to 4, the following commercially available products were prepared as styrene-based elastomers.

[0210] SEPTON 2063: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 13% by mass, weight average molecular weight (Mw) 100,000

[0211] SEPTON 2002: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 30% by mass, weight average molecular weight (Mw) 55,000

[0212] Kraton G1730: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 20% by mass, weight average molecular weight (Mw) 93000

[0213] Kraton G1652: styrene-ethylene-butylene-styrene copolymer (SEBS), styrene unit content 30% by mass, weight average molecular weight (Mw) 75000

[0214] SEPTON 1020: styrene-ethylene-propylene copolymer (SEP), styrene unit content 36% by mass, weight average molecular weight (Mw) 120,000

[0215] SEPTON 4033: styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene unit content 30% by mass, weight average molecular weight (Mw) 88000

[0216] SEPTON 2104: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 65% by mass, weight average molecular weight (Mw) 60,000

[0217] Preparation Example 2-1 (Cyclic Olefin Polymer (B-1))

[0218] (1) Catalyst preparation process

[0219] VO(OC2H5)Cl2 was diluted with cyclohexane to obtain a vanadium catalyst solution having a vanadium concentration of 6.7 mmol / L.

[0220] In addition, ethylaluminum sesquichloride (Al(C2H5) 1.5 Cl 1.5 ) was diluted with cyclohexane to obtain an aluminum catalyst solution. The aluminum concentration of the catalyst solution was 107 mmol / L.

[0221] (2) Polymerization process

[0222] Using a stirred polymerizer (inner diameter 500 mm, reaction volume 100 L), ethylene and tetracyclic [4.4.0.1 2.5 .1 7.10 ]-3-dodecene, and copolymerize them. It should be noted that the adjustment of ethylene and tetracyclo[4.4.0.1 2.5 .1 7.10 The glass transition temperature (Tg) of the cyclic olefin polymer was adjusted by adjusting the ratio of ]-3-dodecene.

[0223] The vanadium catalyst solution was supplied to the polymerization reactor in such a manner that the vanadium catalyst concentration relative to cyclohexane in the polymerization reactor was 0.6 mmol / L. The aluminum catalyst solution was supplied to the polymerization reactor in such a manner that the molar ratio of aluminum to vanadium (Al / V) was 12.0. The polymerization temperature was set to 12° C. The polymerization pressure was set to 3.1 kg / cm 2 G (gauge pressure).

[0224] Thus, ethylene and tetracyclic [4.4.0.1 2.5 .1 7.10 ]-3-dodecene copolymer (cyclic olefin polymer (B-1)). The copolymer was obtained as a solution in cyclohexane (solvent).

[0225] (3) Decalcification process

[0226] The copolymer solution was discharged from the polymerization reactor. A 25% by mass NaOH solution was added to the copolymer solution. The reaction was stopped. In addition, the catalyst residue was removed from the copolymer solution (calcification treatment). The concentration of the copolymer in the solution was 7.7% by mass.

[0227] Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to the copolymer solution. The amount of the stabilizer added was 0.4 parts by mass based on 100 parts by mass of the copolymer.

[0228] Then, a stirring tank (effective volume 1.0 cm 3 ), and the copolymer solution was stirred for 1 hour. The solid content concentration of the copolymer was 5% by mass.

[0229] (4) Desolventization process

[0230] Double-layer tube heater (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21m, heat source 20kg / cm 2 A solution of the copolymer (solid content concentration: 5 mass %) was supplied into a liquid (water vapor) and heated to 180° C. The supply rate was 150 kg / H.

[0231] Next, a double-layer tubular flash dryer (outer tube diameter 2B, inner tube diameter 3 / 4B, length 27m, heat source 20kg / cm 2 G steam), and a flash hopper (volume 200L) to remove cyclohexane from the copolymer solution. In addition, unreacted monomers are removed together with cyclohexane.

[0232] Thus, a cyclic olefin polymer (B-1) in a molten state was obtained. The glass transition temperature (Tg) of the cyclic olefin polymer (B-1) was measured in accordance with JIS K 7122 (2012). As a result, the glass transition temperature (Tg) of the cyclic olefin polymer (B-1) was 105° C. In addition, the weight average molecular weight (measured by gel permeation chromatography in terms of polystyrene) of the cyclic olefin polymer (B-1) was 113,000.

[0233] Preparation Example 2-2 (Cyclic Olefin Polymer (B-2))

[0234] Cyclic olefin polymer (B-2) was obtained by the same method as in Preparation Example 2-1. However, the ethylene and tetracyclic [4.4.0.1 2.5 .1 7.10 The glass transition temperature (Tg) of the cyclic olefin polymer was adjusted by adjusting the composition ratio of 1-3-dodecene.

[0235] The glass transition temperature (Tg) of the cyclic olefin polymer (B-2) was 125° C. The weight average molecular weight (measured by gel permeation chromatography in terms of polystyrene) of the cyclic olefin polymer (B-2) was 116,000.

[0236] Preparation Example 2-3 (Cyclic Olefin Polymer (B-3))

[0237] Cyclic olefin polymer (B-3) was obtained by the same method as in Preparation Example 2-1. However, the ethylene and tetracyclic [4.4.0.1 2.5 .1 7.10 The glass transition temperature (Tg) of the cyclic olefin polymer was adjusted by adjusting the composition ratio of 1-3-dodecene.

[0238] The glass transition temperature (Tg) of the cyclic olefin polymer (B-3) was 65° C. The weight average molecular weight (measured by gel permeation chromatography in terms of polystyrene) of the cyclic olefin polymer (B-3) was 110,000.

[0239] Preparation Example 3-1 (Other olefin polymers (C-1))

[0240] 900 mL of hexane and 90 g of 1-butene were placed in a 2-liter autoclave purged with nitrogen. 1 mmol of triisobutylaluminum was also added to the autoclave. The temperature inside the autoclave was raised to 70°C.

[0241] Next, 0.30 mmol of methylaluminoxane was added to the autoclave, and 0.001 mmol of racemic-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride was added in an amount calculated as Zr.

[0242] Then, propylene was continuously supplied to the autoclave. Then, the total pressure was maintained at 7 kg / cm 2 G, while polymerizing 1-butene and propylene for 30 minutes to obtain a random copolymer of 1-butene and propylene (other olefin polymer (C-1)).

[0243] The autoclave was degassed, and the copolymer (other olefin polymer (C-1)) was recovered with methanol. Then, the copolymer (other olefin polymer (C-1)) was dried at 110° C. for 12 hours under reduced pressure.

[0244] The melting point (Tm) of the other olefin polymer (C-1) was measured in accordance with JIS K 7122 (2012). As a result, the melting point (Tm) of the other olefin polymer (C-1) was 78.3° C. The weight average molecular weight (Mw) of the other olefin polymer (C-1) was 300,000.

[0245] Preparation Example 3-2 (Other olefin polymers (C-2))

[0246] The following commercially available products were prepared as other olefin-based polymers (C-2).

[0247] Trade name Vistamaxx 6102: propylene-ethylene copolymer (PER), styrene unit content 0 mass%, weight average molecular weight (Mw) 320,000, melting point 107°C, manufactured by ExxonMobil Japan GK

[0248] Preparation Example 3-3 (Other olefin polymers (C-3))

[0249] The following commercially available products were prepared as other olefin-based polymers (C-3).

[0250] Trade name Vistamaxx 3020FL: propylene-ethylene copolymer (PER), styrene unit content 0 mass %, weight average molecular weight (Mw) 370000, melting point 64°C, manufactured by ExxonMobil Japan GK

[0251] 2. Preparation of resin composition

[0252] Example 1 (Low dielectric resin composition (D-1))

[0253] As resin components, 50 parts by mass of SEPTON 2063 (SEPS, Mw 100,000, styrene unit content 13%) and 50 parts by mass of cyclic olefin polymer (B-1) were prepared.

[0254] To the resin component, maleic anhydride (MAH) was added as a modifier in a ratio of 1 part by mass based on 100 parts by mass of the total amount of the resin component.

[0255] Furthermore, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (peroxide, modified initiator) was added to the resin component. The amount of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane added was 0.6 parts by mass based on 100 parts by mass of the total amount of the resin component.

[0256] Then, the resin component was melt-kneaded at 230° C. using a vented twin-screw kneading extruder. Thus, a low dielectric resin composition (D-1) was obtained. Hereinafter, the low dielectric resin composition is simply referred to as a resin composition.

[0257] The resin composition (D-1) was cooled and pelletized. Then, 100 parts by mass of the pellets of the resin composition (D-1) were dissolved in 400 parts by mass of toluene under a heating environment. Thus, a solution of the resin composition (D-1) (solid content concentration 20% by mass) was obtained.

[0258] Examples 2 to 13 and Comparative Examples 1 to 9 (resin compositions (D-2) to (D-22))

[0259] Except for changing the formulations shown in Tables 1 to 4, resin compositions (D-2) to (D-21) were obtained by the same method as in Example 1. In addition, solutions (solid content concentration 20% by mass) of resin compositions (D-2) to (D-21) were obtained by the same method as in Example 1. It should be noted that in Example 12, no modifier was added.

[0260] 3. Evaluation

[0261] (1) Determination of relative dielectric constant and dielectric loss tangent

[0262] The solution of the resin composition was applied onto a release film (polyethylene terephthalate film, 100 μm thick), and dried at 100° C. for 1 minute. Thus, a dry coating film (about 60 μm thick) of the resin composition was obtained.

[0263] The dried coating film was formed into a strip shape, and the relative dielectric constant and dielectric loss tangent of the dried coating film were measured according to JIS R1641 (2007). It should be noted that a cavity resonator (vector network analyzer HP8510B (Keysight Technologies)) was used in the measurement. In addition, the measurement frequency was set to 10 GHz.

[0264] (2) Compatibility (affinity with thermosetting resin)

[0265] Polyphenylene ether (hereinafter referred to as PPE) was prepared as a thermosetting resin, and PPE was dissolved in toluene to obtain a PPE solution.

[0266] The PPE solution was mixed with the above-mentioned resin composition solution to obtain a mixed solution. The mass ratio of PPE to the resin composition (PPE:resin composition) was set to 7:3.

[0267] The mixed solution was applied to a glass plate and dried at 100° C. for 1 minute to obtain a dry coating film (film thickness: about 30 μm) of the mixed resin.

[0268] The haze of the dried coating film was measured in accordance with JIS K7136 (2000). It should be noted that a turbidity meter (NDH 4000 (manufactured by Nippon Denshoku Industries)) was used for the measurement. The transparency of the dried coating film was evaluated by the haze value and visual observation. The evaluation criteria are described below.

[0269] 5: The coating film is homogeneous as a whole and has a haze of less than 25.

[0270] 4: The entire coating film is homogeneous and has a haze of 25 or more.

[0271] 3: Phase separation occurred in the coating film. The phase separation part was evenly distributed in the entire coating film.

[0272] 2: Phase separation occurred in the coating film. The phase separation part is uneven. The maximum length of the uneven part is less than 1 cm.

[0273] 1: Phase separation occurred in the coating film. The phase separation portion was non-uniform. The maximum length of the non-uniform portion was 1 cm or more.

[0274] It should be noted that, if the affinity between the resin composition and the thermosetting resin is improved, the adhesiveness is also improved. In addition, if the affinity between the resin composition and the thermosetting resin is improved, the strength of the molded product is also improved.

[0275] (3) Heat resistance

[0276] 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (trade name PERHEXYNE 25B, manufactured by NOF Corporation) was added as a thermal initiator to the resin composition solution. The solid content of the thermal initiator was 3 parts by mass based on 100 parts by mass of the total solid content of the resin component of the resin composition.

[0277] Next, the solution of the resin composition to which the thermal initiator was added was placed in a Teflon (registered trademark) dish and dried at 100° C. for 1 minute. Thus, a dry coating film (film thickness of about 100 μm) of the resin composition was obtained.

[0278] The dried coating film of the resin composition was heat treated at 200° C. for 3 hours. Then, the shear storage elastic modulus (G′) of the dried coating film of the resin composition was measured. It should be noted that a viscoelasticity measuring device (MCR302 (manufactured by Anton Paar Japan)) was used for the measurement. In addition, the measurement conditions are as follows.

[0279] Temperature range: 0℃~200℃

[0280] Heating rate: 2℃ / min

[0281] Working conditions: Shear mode

[0282] Frequency: 1Hz

[0283] Then, the heat resistance of the dried coating film was evaluated by the shear storage elastic modulus (G'). The evaluation criteria are described below.

[0284] ○: The shear storage elastic modulus (G') at 200°C is 1500 Pa or more.

[0285] △: The shear storage modulus (G') at 200°C is 1000 Pa or more and less than 1500 Pa.

[0286] ×: The shear storage elastic modulus (G') at 200°C is less than 1000 Pa.

[0287] (4) Solubility in solvents

[0288] The solubility of the resin composition in toluene was evaluated by visually checking a solution of the resin composition (solid content concentration: 20% by mass, toluene solution). The evaluation criteria are described below.

[0289] ○: When the resin composition and the solvent are stirred and left to stand, the solution is a uniform liquid.

[0290] △: The mixture of the resin composition and the solvent is in a uniform gel state.

[0291] ×: Precipitates were observed in the mixture of the resin composition and the solvent. In addition, the mixture was not uniform as a whole.

[0292] [Table 1]

[0293]

[0294] [Table 2]

[0295]

[0296] [Table 3]

[0297]

[0298] [Table 4]

[0299]

[0300] The details of the abbreviations in the table are described below.

[0301] Styrene unit content: content ratio of structural units derived from styrene (mass %)

[0302] SEPTON 2063: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 13% by mass, weight average molecular weight (Mw) 100,000, manufactured by KURARAY SEPTON 2002: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 30% by mass, weight average molecular weight (Mw) 55,000, manufactured by KURARAY

[0303] Kraton G1730: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 20% by mass, weight average molecular weight (Mw) 93,000, manufactured by Kraton Polymer Japan Corporation

[0304] Kraton G1652: styrene-ethylene-butylene-styrene copolymer (SEBS), styrene unit content 30% by mass, weight average molecular weight (Mw) 75,000, manufactured by Kraton Polymer Japan Corporation

[0305] SEPTON 1020: styrene-ethylene-propylene copolymer (SEP), styrene unit content 36% by mass, weight average molecular weight (Mw) 120,000, manufactured by KURARAY

[0306] SEPTON 4033: styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene unit content 30% by mass, weight average molecular weight (Mw) 88,000, manufactured by KURARAY SEPTON 2104: styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 65% by mass, weight average molecular weight (Mw) 60,000, manufactured by KURARAY

[0307] MAH: Modifier, carboxyl-containing monomer maleic anhydride

[0308] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but it is only for illustration and is not to be construed as limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the appended claims.

[0309] Industrial Applicability

[0310] The low-dielectric resin composition, adhesion-imparting agent, low-dielectric adhesive composition, low-dielectric adhesive molded product, low-dielectric adhesive, and laminate of the present invention can be suitably used in the field of circuit boards.

Claims

1. A low dielectric resin composition comprising a polyolefin resin, The polyolefin resin contains a styrene elastomer (A) and a cyclic olefin polymer (B) having an alicyclic ring in the main chain. The content ratio of the styrene elastomer (A) is 30 parts by mass or more and 89 parts by mass or less based on 100 parts by mass of the total amount of the styrene elastomer (A) and the cyclic olefin polymer (B).

2. The low dielectric resin composition according to claim 1, wherein The weight average molecular weight of the styrene-based elastomer (A) is 70,000 to 110,000.

3. The low dielectric resin composition according to claim 1, wherein The styrene-based elastomer (A) contains a structural unit derived from styrene, and the content ratio of the structural unit derived from styrene is 10% by mass or more and 40% by mass or less based on the total amount of the styrene-based elastomer (A).

4. The low dielectric resin composition according to claim 1, wherein The styrene-based elastomer (A) does not contain a structural unit derived from butene.

5. The low dielectric resin composition according to claim 1, wherein The glass transition temperature of the cyclic olefin polymer (B) is 100° C. or higher and 140° C. or lower.

6. The low dielectric resin composition according to claim 1, wherein The polyolefin resin is modified with a monomer containing a functional group.

7. The low dielectric resin composition according to claim 6, wherein The functional group-containing monomer includes a carboxyl group-containing monomer. 8 . An adhesion-imparting agent comprising the low dielectric resin composition according to claim 1 .

9. A low dielectric adhesive composition comprising a thermosetting resin and the adhesion-imparting agent according to claim 8, The thermosetting resin includes at least one selected from the group consisting of epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin having unsaturated double bonds, and liquid crystal polymer. 10 . A low-dielectric adhesive molded product comprising a cured product of the low-dielectric adhesive composition according to claim 9 .

11. A laminate comprising: An insulating layer comprising the low dielectric adhesive molded article according to claim 10; and A conductive layer is disposed on at least one surface of the insulating layer. 12 . A low dielectric adhesive comprising the low dielectric resin composition according to claim 1 .

13. A laminate comprising: Insulation layer; a conductor layer disposed opposite to the insulating layer; and an adhesive layer disposed between the insulating layer and the conductive layer and bonding the insulating layer and the conductive layer together, The adhesive layer includes the low dielectric adhesive according to claim 12 .

14. A laminate comprising: 1st conductor layer; a second conductor layer disposed opposite to the first conductor layer; and an adhesive layer disposed between the first conductive layer and the second conductive layer and bonding the first conductive layer and the second conductive layer together; The adhesive layer includes the low dielectric adhesive according to claim 12 .

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