CN115135496A - Structural body - Google Patents

Abstract

[ problem ] to provide a structure in which the front and back sides of a multilayer structure can be easily distinguished, and a resin layer is less likely to have film marks when a second film is peeled. [ solution ] the structure of the present invention is provided with a first film, a resin layer, and a second film in this order, and is characterized in that the difference between the trouser tear strength of the first film and the trouser tear strength of the second film is-0.05N or less or +0.05N or more, the difference between the haze values of the first film and the second film is-5% or less or + 5% or more, or the difference between the L, a, b values in the Lab color space measured from the first film side of the structure and the L, a, b values in the Lab color space measured from the second film side of the structure satisfies a specific condition.

Description

Structural body

Technical Field

The present invention relates to a structure, and more particularly, to a structure including a first film and a resin layer, or a structure including a first film, a resin layer, and a second film in this order.

Background

As a method for manufacturing a printed wiring board, a method for manufacturing a printed wiring board based on a build-up (build-up) method in which insulating layers and conductor layers are alternately stacked is widely used. In the production method by the build-up method, the insulating layer is generally formed by thermally curing a curable resin composition as a curable resin layer.

In recent years, it has also been proposed to form an insulating layer by a dry film method, which is used in the above-described manufacturing method by a build-up method. The dry film is a structure having a curable resin layer obtained by applying a liquid curable resin composition adjusted to a predetermined viscosity to a region on the surface of a separately prepared first film and then drying the applied composition. In addition, the dry film is usually further laminated with a second film to protect the surface of the curable resin layer opposite to the first film.

In the above-described structure, since there is a sequence of steps in which the second film is peeled off first, the first film is peeled off after being laminated on the substrate, or after being cured, a method for distinguishing which film of the first film and the second film is peeled off is required. However, in the above structure, when both the first film and the second film are transparent, it is difficult to distinguish the films, and there is a possibility that the peeling order of the first film and the second film may be wrong. In particular, if films of the same specification are used for the first film and the second film, this tendency is remarkable, and in this case, there is also a problem that linear marks (hereinafter referred to as "film marks") are generated in the resin layer due to the relationship with the first film when the second film is peeled from the structure. Therefore, as a method for easily distinguishing the front and back surfaces of the structure, for example, it is proposed to provide a colored layer on one surface so that the color difference between the front and back surfaces can be visually recognized (see patent document 1).

Conventionally, chip-type devices (chip components) such as semiconductor elements and electronic components are sealed by a transfer molding method using a powder epoxy resin composition, an potting method using a liquid epoxy resin composition, a silicone resin, or the like, a dispensing method, a printing method, or the like. However, in order to be suitable for mounting on a device with high integration and efficiently manufacture a device such as a Surface Acoustic Wave (SAW) device or a crystal device, which needs to be hollow after sealing, it is necessary to seal and package the device on a substrate having a plurality of chip-type devices collectively.

For example, patent document 2 proposes a thermosetting resin composition containing (a) a crosslinkable elastomer, (B) an epoxy resin, (C) an epoxy resin curing agent, and (D) an inorganic filler, as a composition capable of sealing together. In recent years, it has been proposed to perform collective sealing by a dry film type.

The dry film is generally a structure having a curable resin layer on a first film. In general, the above-described structure can be produced by applying a liquid curable resin composition to a first film to which tension is applied, and then drying the composition to form a curable resin layer.

Incidentally, the first film used for the structure is used by unwinding the film taken up onto a roll, but at this time, there is a problem that the film is wrinkled or slackened. To solve such problems, the following solutions are proposed: the rolling circumferential lengths D1 to D14 of the respective portions when the film roll is divided into equal parts in the width direction 14 satisfy a specific condition, and the difference (Tm) between the maximum thicknesses of the film thicknesses T1 to T14 of the respective portions measured straightly in the width direction of the film roll divided into equal parts 14 satisfies a specific condition (see patent document 3).

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2010-069760

Patent document 2: japanese patent laid-open publication No. 2015-166403

Patent document 3: japanese patent laid-open publication No. 2016-44035

Disclosure of Invention

Problems to be solved by the invention

< problem of first embodiment >

However, in the method of patent document 1, since the coloring layer is provided as a layer different from the thermoplastic films laminated on both surfaces of the core material, there is a problem that the number of steps increases and the manufacturing cost increases.

Accordingly, an object of the first aspect of the present invention is to provide a structure in which a first film and a second film of a multilayer structure can be easily distinguished from each other, and a resin layer is less likely to be scratched when the second film is peeled.

< problem of the second embodiment >

Further, the following problems are found in the structures such as patent documents 2 and 3: in the case of a first film, longitudinal wrinkles may be generated when tension is applied to the first film. On the other hand, when the thickness of the resin layer is small, even if wrinkles occur in the first film, the resin layer having a small thickness variation can be formed to follow the wrinkles. However, when the thickness of the resin layer is as thick as, for example, 50 μm or more, the liquid curable resin composition applied to the wrinkle valleys of the first film accumulates when the resin layer is formed on the first film, and as a result, a problem has been found that a resin layer having a large variation in thickness is formed after drying.

Accordingly, a second aspect of the present invention is directed to a structure including a resin layer having a thickness of 50 μm or more and small variations in thickness on a first film.

Means for solving the problems

< means of the first embodiment >

The present inventors have conducted extensive studies to achieve the above-described object of the first aspect, and as a result, have found that the haze or each of the L, a, or b values can be easily distinguished from the interior of the structure by adjusting the haze of the first and second films themselves, or the L, a, or b values in the Lab color space measured from the first film side of the structure, and the L, a, or b values in the Lab color space measured from the second film side of the structure.

Further, the present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the occurrence of film marks can be suppressed by adjusting the trouser tear forces of the first film and the second film to impart a certain or more difference in the respective trouser tear forces.

That is, the structural body of the first aspect which is an object of the first aspect of the present invention is characterized by comprising a first film, a resin layer, and a second film in this order,

the difference between the trouser tear force of the first film and the trouser tear force of the second film is less than-0.05N or more than +0.05N,

the difference in haze between the first film and the second film is-5% or less or + 5% or more.

A structure of a second aspect for the object of the first aspect of the present invention is characterized by comprising a first film, a resin layer, and a second film in this order,

the difference between the trouser tear force of the first film and the trouser tear force of the second film is less than-0.05N or more than +0.05N,

the difference between the L, a, b values in the Lab color space measured from the first film side of the structure and the L, a, b values in the Lab color space measured from the second film side of the structure satisfies at least one of the following conditions (i) to (iii),

(i) the difference of L is less than-0.1 or more than + 0.1;

(ii) the difference of a is less than-0.1 or more than + 0.1;

(iii) the difference of b is less than-1 or more than + 1.

In the first and second aspects for the object of the first aspect of the present invention, the trouser tear force of the second film is preferably smaller than the trouser tear force of the first film.

In the first and second aspects of the object of the first aspect of the present invention, the resin layer is preferably a curable resin layer.

In the first and second aspects directed to the object of the first aspect of the present invention, the first film is preferably selected from a polyester film and a polyolefin film.

In the first and second aspects directed to the object of the first aspect of the present invention, the second film is preferably selected from a polyester film and a polyolefin film.

< means of the second embodiment >

The present inventors have conducted extensive studies to achieve the object of the second aspect, and as a result, have found that when a resin layer having a thickness of 50 μm or more is formed, a resin layer having a small variation in thickness can be formed by adjusting the trouser tear force of the first film and adjusting the thickness of the first film. The present invention is based on the above technical idea.

The structural body of the embodiment of the present invention is characterized by comprising a first film and a resin layer,

the thickness of the first film is 30 [ mu ] m or more,

the trouser tear force of the first film is 0.1N or more,

the thickness of the resin layer is 50 μm or more,

the resin layer is a curable resin layer.

In an aspect directed to the object of the second aspect of the present invention, the curable resin layer preferably contains a thermosetting resin and a curing agent.

In an aspect to the object of the second aspect of the present invention, the thermosetting resin is preferably an epoxy compound.

In an aspect directed to the object of the second aspect of the present invention, the resin layer is preferably a curable resin layer.

In an aspect to the object of the second aspect of the present invention, the first film is preferably selected from the group consisting of a polyester film, a polyolefin film, and a polyimide film.

In an aspect directed to the object of the second aspect of the present invention, the variation in thickness of the first film is preferably ± 10% or less.

ADVANTAGEOUS EFFECTS OF INVENTION

< effects of the first embodiment >

According to the present invention, it is possible to provide a structure in which the front and back surfaces of the structure having a multilayer structure can be easily distinguished, and a resin layer is less likely to have a film mark when a second film is peeled.

The reason why the generation of the film mark can be suppressed by adjusting the trouser tear force of the first film and the second film to give a certain difference or more to each trouser tear force is not necessarily clear, but is presumed as follows. That is, if the difference in the tear force in the pants-shape is given, the load applied to the resin layer at the time of peeling the film is different from that at the time of not giving the difference in the tear force, which is suitable. As a result, it is considered that there is a difference in the ease of forming a film mark on the resin layer. However, the present invention is not limited to this.

< effects of the second embodiment >

Further, according to the present invention, there can be provided a structure including a resin layer having a thickness of 50 μm or more and small variations in thickness on a first film.

The reason why the resin layer having a small variation in thickness can be formed by adjusting the trouser tear force of the first film and adjusting the thickness of the first film is not necessarily clear, but is presumed as follows. Namely, it is presumed that: by the above adjustment, the surface state of the first film becomes appropriate, and the force is received even when tension is applied to the first film, so that wrinkles are less likely to occur, and as a result, the resin layer formed on the first film is easily formed, and variation in the thickness of the resin layer can be suppressed. However, this is only an assumption and is not limited thereto.

Drawings

Fig. 1 is a schematic cross-sectional view showing one embodiment of the structure of the present invention.

Fig. 2 is a schematic cross-sectional view showing one embodiment of the structure of the present invention.

Detailed Description

< description of the first embodiment >

< Structure >

The structure of the present invention includes a first film, a resin layer, and a second film in this order, and the first film and the second film satisfy specific conditions described below. In the present invention, when the first film and the second film satisfy specific conditions described later, it is possible to provide a structure in which the front and back sides of the structure having a multilayer structure can be easily distinguished, and the resin layer is less likely to have a film mark when the second film is peeled.

The structure of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing one embodiment of the structure of the present invention. As shown in fig. 1, the structure 1 includes a first film 10, a resin layer 20 provided on one surface of the first film 10, and a second film 30 provided on the surface of the resin layer 20 opposite to the surface provided with the first film 10. Hereinafter, each constituent element constituting the structure of the present invention will be described.

[ first film and second film ]

In the present invention, the difference between the trouser tear strength and the haze of the first film and the second film, or the difference between the L, a, and b values in the Lab color space may be within the ranges described below.

The first film in the present invention has a function of supporting the resin layer of the structure, and is a film coated with a resin composition at the time of forming the resin layer. In the present invention, the term "film" means a film which is bonded to at least a resin layer when the resin layer side of a structure is laminated by heating or the like to be in contact with a substrate such as a substrate and integrally molded, and is preferably peeled from the structure after the resin layer is cured. Examples of the first film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene films and polypropylene films, fluororesin films such as polytetrafluoroethylene films, polyimide films, polyamideimide films, and films made of thermoplastic resins such as polystyrene films. Among these, polyester films and polyolefin films can be suitably used in view of heat resistance, mechanical strength, handling properties, and the like. The surface of the first film on which the resin layer is provided may be subjected to a mold release treatment or a roughening treatment, or may be formed with a sputtered or extra thin copper foil and an adhesive layer.

The thickness of the first film is not particularly limited and may be appropriately selected depending on the application. The thickness of the first film is preferably 12 μm to 125 μm, more preferably 15 μm to 75 μm, from the viewpoints of mechanical strength, handling properties, and the like.

The second film in the present invention is a film provided on the surface of the resin layer of the structure opposite to the first film for the purpose of preventing dust and the like from adhering to the surface of the resin layer and improving the handling properties. In particular, the present invention refers to a film which is peeled from a structure before lamination when the resin layer side of the structure is laminated by heating or the like so as to be in contact with a substrate such as a substrate and the like and integrally molded. As the second film, for example, a film made of a thermoplastic resin exemplified in the above-described first film can be used. Among these, polyester films and polyolefin films are preferable in terms of heat resistance, mechanical strength, handling properties, and the like. The surface of the second film on which the resin layer is provided may be subjected to a mold release treatment.

The thickness of the second film is not particularly limited and may be appropriately selected depending on the application. The thickness of the second film is preferably 10 μm to 100 μm, more preferably 15 μm to 50 μm, from the viewpoints of mechanical strength, handling properties, and the like.

In the structure of the present invention, the difference between the trouser tear force of the first film and the trouser tear force of the second film (═ the trouser tear force of the first film "-" the trouser tear force of the second film ") is-0.05N or less or +0.05N or more, preferably-0.1N or less or +0.1N or more, more preferably-0.3N or more and-0.1N or less or +0.1N or more and +0.3N or less, and still more preferably +0.1N or more and +0.3N or less. From the viewpoint of being less likely to have film marks, it is preferable that the second film has a trouser tear force smaller than that of the first film.

In the present invention, the trouser tear force of the first film and the second film is measured in accordance with JIS K7128-1: 1998 "tear Strength test method for Plastic-films and sheets-first part: "trouser tear method" is a value measured under the following measurement conditions using a tensile tester (EZ-SX, manufactured by Shimadzu corporation). However, in the present invention, only the machine direction (MD direction) is measured with respect to the measurement direction regardless of the presence or absence of anisotropy based on the direction.

(measurement conditions)

Temperature and humidity of the laboratory: 23 +/-2 ℃ and 50 +/-15 percent

Test piece size: 150mm x 50mm

Cut length in the center of the test piece: 75 +/-1 mm

Test speed: 200mm/min

Distance between the grips of the test piece: 75mm

The trouser tear force of the first and second films can be adjusted to be within a desired range by adjusting the kind of thermoplastic resin of the first and second films, the stretch ratio at the time of film production, the thickness of the film, the breaking strength of the film, the roughness of the surface, and the like.

In the structure of the present invention, the difference between the haze of the first film and the haze of the second film (i.e., "the haze of the first film" - "the haze of the second film") is-5% or less or + 5% or more, and is preferably-8% or less or + 8% or more, more preferably-85% or more and-8% or less or + 8% or more and + 85% or less, from the viewpoint of making it easier to distinguish the front surface from the back surface of the structure having a multilayer structure. The haze of the first film and the second film can be adjusted to a desired range by adjusting the roughness of the surfaces of the first film and the second film, the addition and kind of the colorant, the kind of the thermoplastic resin, the stretch ratio at the time of film production, the thickness of the film, and the like. By making the difference in haze between the first film and the second film satisfy the above conditions, the front and back surfaces of the structure of the multilayer structure can be easily distinguished.

In the present invention, the haze of the first film and the second film is a value measured by a haze meter according to ASTM D1003 for the film itself.

Alternatively, in the structure of the present invention, the difference between the L, a, b values measured from the first membrane side of the structure and the L, a, b values measured from the second membrane side of the structure ("L, a, b values measured from the first membrane side of the structure") in the Lab color space satisfies at least one of the following conditions (i) to (iii).

(i) The difference in L value is-0.1 or less or +0.1 or more, and is preferably-10 or less or +10 or more, more preferably-30 or more and-15 or less or +15 or more and +30 or less, from the viewpoint of making it easier to distinguish the front side and the back side of the structure having a multilayer structure.

(ii) The difference in value a is-0.1 or less or +0.1 or more, and is preferably-0.3 or less or +0.3 or more, more preferably-30 or more and-0.3 or less or +0.3 or more and +30 or less, from the viewpoint of making it easier to distinguish the front side from the back side of the multilayer structure.

(iii) The difference in b is-1 or less or +1 or more, and is preferably-2 or less or +2 or more, more preferably-10 or more and-2 or less or +2 or more and +10 or less, from the viewpoint of making it easier to distinguish the front side and the back side of the structure having a multilayer structure.

The L value, a value, b value in the Lab color space measured from the first film side of the structure and the L value, a value, b value in the Lab color space measured from the second film side of the structure can be adjusted to be within a desired range by adjusting the roughness of the surfaces of the first film and the second film, the amount and kind of the colorant added, the kind of the thermoplastic resin, the stretch ratio at the time of film production, the thickness of the film, and the like. The difference between the L, a, b values in the Lab color space measured from the first film side of the structure and the L, a, b values in the Lab color space measured from the second film side of the structure satisfies the above condition, and thus the front and back surfaces of the structure having the multilayer structure can be easily distinguished. Among them, from the viewpoint of easier discrimination, it is particularly preferable that the difference described in (i), i.e., the difference in L value, satisfies the above condition.

In the present invention, L, a, b values in the Lab color space measured from the second film side of the structure and L, a, b values in the Lab color space measured from the first film side of the structure are measured using a spectrophotometer under the following measurement conditions.

(measurement conditions)

Reflection mode

Specular reflection light processing

Measurement of diameter: SAV (3mm)

UV conditions: 100% full of

Visual field: 10 degree

65 degree of incident light

Measurement method: SCE (excluding specular component)

Substrate: black lining paper (L value: 27.3, a value 0.7, b value 2.0)

[ resin layer ]

The resin layer is a layer located between the first film and the second film of the structure, and is preferably a curable resin layer. The curable resin layer is a dried coating film obtained by drying the curable resin composition, and may be a thermosetting resin layer cured by heating, a photocurable resin layer cured by light irradiation, or a thermosetting/photocurable resin layer cured by heating and cured by light irradiation.

(curable resin composition)

The curable resin composition preferably contains at least one of a thermosetting resin and a photocurable resin, and may further contain other components.

(thermosetting resin)

When the curable resin composition contains a thermosetting resin, the heat resistance of the cured product is improved, and the adhesion to the substrate is improved. Examples of the thermosetting resin include an amino resin such as melamine resin, benzoguanamine resin, melamine derivative, and benzoguanamine derivative, an isocyanate compound, a blocked isocyanate compound, a cyclic carbonate compound, an epoxy compound, an oxetane compound, an episulfide resin, bismaleimide, and a carbodiimide resin. Among these, a compound having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter, simply referred to as cyclic (thio) ether groups) in the molecule is preferable. The thermosetting resin may be used alone in 1 kind or in combination of 2 or more kinds.

Such a thermosetting resin having a cyclic (thio) ether group in the molecule is a compound having either or both of a cyclic ether group or a cyclic thioether group having a3, 4 or 5-membered ring in the molecule, and examples thereof include an epoxy compound, a polyfunctional oxetane compound, and an episulfide resin. Among these, epoxy compounds are preferred.

Examples of the epoxy compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin, etc., biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, tetraphenolethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl methacrylate copolymer type epoxy resin, epoxy resin copolymer of cyclohexylmaleimide and glycidyl methacrylate, Epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, trimethylolpropane polyglycidyl ether, phenyl-1, 3-diglycidyl ether, biphenyl-4, 4' -diglycidyl ether, 1, 6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2, 3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

Examples of commercially available epoxy resins include jER828, 806, 807, YX8000, YX8034, 834, YD-128 manufactured by Nippon Steel Chemical & Material Co., Ltd, YDF-170, ZX-1059, ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC, and RE-306 manufactured by Nippon Chemical Co., Ltd.

Examples of the polyfunctional oxetane compound include bis [ (3-methyl-3-oxetanylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, (3-methyl-3-oxetanylmethoxy) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, and mixtures thereof, Polyfunctional oxetanes such as oligomers and copolymers thereof; and etherates of oxetanol and hydroxyl group-containing resins such as novolak resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, and silsesquioxanes. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate, and the like can be mentioned.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol a type episulfide resins and the like. Alternatively, an episulfide resin or the like in which an oxygen atom of an epoxy group of a novolac epoxy resin is replaced by a sulfur atom by the same synthesis method can be used.

Examples of the amino resin such as a melamine derivative and a benzoguanamine derivative include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylolurea compounds.

As the isocyanate compound, a polyisocyanate compound may be compounded. Examples of the polyisocyanate compound include aromatic polyisocyanates such as 4, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, naphthalene-1, 5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and 2, 4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and addition products of the isocyanate compounds, biuret products, isocyanurate products, and the like mentioned above.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent may be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the polyisocyanate compounds described above. Examples of the isocyanate blocking agent include: a phenolic capping agent; a lactam-based blocking agent; an active methylene-based blocking agent; an alcohol-based blocking agent; an oxime-based blocking agent; a thiol-based blocking agent; an amide-based blocking agent; an imide-based end-capping agent; an amine-based blocking agent; an imidazole-based capping agent; and an imine-based blocking agent.

(Photocurable resin (radical polymerization))

As the photocurable resin, a compound having 1 or more ethylenically unsaturated bonds in the molecule is particularly preferably used. As the compound having an ethylenically unsaturated bond, a conventional photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like is used.

Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of the (meth) acrylate-based oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, bisphenol epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and polybutadiene-modified (meth) acrylate. In the present specification, the term (meth) acrylate refers to a general term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Examples of the photopolymerizable vinyl monomer include known and customary ones, for example, styrene derivatives such as styrene, chlorostyrene, and α -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, and vinyl benzoate; vinyl ethers such as vinyl isobutyl ether, vinyl n-butyl ether, vinyl t-butyl ether, vinyl n-pentyl ether, vinyl isoamyl ether, vinyl n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, and triethylene glycol monomethyl vinyl ether; (meth) acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymmethacrylamide, N-ethoxymethacrylamide and N-butoxymethacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; esters of (meth) acrylic acid such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like; alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; alkylene polyol poly (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri (meth) acrylate; poly (meth) acrylates such as hydroxypivalyl hydroxypivalate di (meth) acrylate; isocyanurate type poly (meth) acrylates such as tris [ (meth) acryloyloxyethyl ] isocyanurate, and the like.

(Photocurable resin (cationic polymerization))

As the photocurable resin, an alicyclic epoxy compound, a vinyl ether compound, or the like can be suitably used. Among them, examples of the alicyclic epoxy compound include 3,4,3 ', 4' -diepoxybicyclohexane, 2-bis (3, 4-epoxycyclohexyl) propane, 2-bis (3, 4-epoxycyclohexyl) -1, 3-hexafluoropropane, bis (3, 4-epoxycyclohexyl) methane, 1- [1, 1-bis (3, 4-epoxycyclohexyl) ] ethylbenzene, bis (3, 4-epoxycyclohexyl) adipate, 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate, (3, 4-epoxy-6-methylcyclohexyl) methyl-3 ', 4' -epoxy-6-methylcyclohexanecarboxylate, ethylene-1, 2-bis (3, 4-epoxycyclohexanecarboxylic acid) ester, an alicyclic epoxy compound having an epoxy group such as epoxycyclohexane, 3, 4-epoxycyclohexylmethyl alcohol, 3, 4-epoxycyclohexylethyltrimethoxysilane, and the like.

Examples of the vinyl ether compound include cyclic ether type vinyl ethers such as isosorbide divinyl ether and oxanorbornene divinyl ether (vinyl ethers having a cyclic ether group such as an oxirane ring, an oxetane ring or an oxetane ring); aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1, 4-butanediol divinyl ether, cyclohexane divinyl ether and cyclohexanedimethanol divinyl ether, and vinyl ether compounds having a substituent such as an alkyl group or an allyl group at the α -position and/or the β -position.

(alkali-soluble resin)

The curable resin composition may contain an alkali-soluble resin. As the alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. In addition to improving the adhesion to the substrate, the use of a carboxyl group-containing resin is particularly preferable from the viewpoint of developability. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond.

(1) A carboxyl group-containing photosensitive resin obtained by reacting (meth) acrylic acid with an epoxy resin and adding a 2-membered acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like to a hydroxyl group present in a side chain.

(2) A carboxyl group-containing photosensitive resin obtained by further epoxidizing the hydroxyl group of an epoxy resin with epichlorohydrin, reacting the obtained polyfunctional epoxy resin with (meth) acrylic acid, and adding a 2-membered acid anhydride to the resulting hydroxyl group.

(3) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid or other polybasic acid anhydride with respect to the alcoholic hydroxyl group of the obtained reaction product.

(4) A carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule, such as bisphenol a, bisphenol F, bisphenol S, novolak-type phenol resins, polyparahydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes, with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.

(5) A carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.

(6) A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by polyaddition reaction of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(7) In the synthesis of a carboxyl group-containing urethane resin based on a polyaddition reaction of a carboxyl group-containing diol compound such as diisocyanate, dimethylolpropionic acid or dimethylolbutyric acid with a diol compound, a carboxyl group-containing urethane resin in which terminal (meth) acrylation is performed by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) acrylate.

(8) In the synthesis of a carboxyl group-containing urethane resin based on a polyaddition reaction of a diisocyanate, a carboxyl group-containing diol compound and a diol compound, a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, is added to carry out terminal (meth) acrylation of the carboxyl group-containing urethane resin.

(9) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.

(10) A carboxyl group-containing photosensitive resin obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid with an oxetane resin to add a 2-membered acid anhydride to the primary hydroxyl group formed, and further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate to the obtained carboxyl group-containing polyester resin.

(11) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in 1 molecule to the carboxyl group-containing resins (1) to (10).

The carboxyl group-containing resin has a plurality of carboxyl groups in the side chain of the polymer main chain, and therefore can be developed with a dilute aqueous alkali solution.

The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is 40mgKOH/g or more, alkali development is easy, and when it is 200mgKOH/g or less, a normal resist pattern is easily drawn.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is preferably in the range of usually 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tack free property, the development resistance of the coating film after exposure, and the resolution become good. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is excellent.

The carboxyl group-containing resin may be used other than the above-mentioned ones, and may be used singly or in combination of two or more.

As the phenol resin, phenol resins having various skeletons synthesized using a compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton or both of them, or a compound having a phenolic hydroxyl group, for example, phenol, o-cresol, p-cresol, m-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, 5-xylenol, catechol, resorcinol, hydroquinone, methyl hydroquinone, 2, 6-dimethyl hydroquinone, trimethyl hydroquinone, pyrogallol, phloroglucinol, and the like can be used.

For example, known and conventional phenol resins such as phenol novolac resins, alkylphenol novolac resins, bisphenol a novolac resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, polyvinyl phenols, bisphenol F, bisphenol S type phenol resins, poly-p-hydroxystyrene, condensates of naphthol and aldehyde, and condensates of dihydroxynaphthalene and aldehyde can be used. They may be used alone or in combination of 2 or more.

In the present invention, as the alkali-soluble resin, any one of a carboxyl group-containing resin and a phenol resin or a mixture thereof can be used.

When a material containing no ethylenically unsaturated group is used as the alkali-soluble resin, the above-mentioned photocurable resins are preferably used in combination. The photocurable resin is photocured by irradiation with active energy rays, and promotes dissolution of the alkali-soluble resin in an aqueous alkali solution. In either case, one or more photocurable resins may be used.

(thermoplastic resin)

In order to improve the mechanical strength of the obtained cured coating film, the curable resin composition may further contain a thermoplastic resin. The thermoplastic resin is preferably soluble in a solvent. When soluble in a solvent, the flexibility of the dry film is improved, and the generation of cracks and dusting can be suppressed. Examples of the thermoplastic resin include a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensate of epichlorohydrin and various 2-functional phenolic compounds, a phenoxy resin in which a hydroxyl group present in a hydroxy ether portion of a skeleton thereof is esterified with various acid anhydrides or acid chlorides, a polyvinyl acetal resin, a polyamide resin, a polyamideimide resin, a block copolymer, a polymer resin having a glass transition temperature of 20 ℃ or less and a weight average molecular weight of 1 ten thousand or more, and the like. The polymer resin is preferably an acrylate copolymer. The thermoplastic resin can be used alone in 1 or more than 2 combination.

(curing agent)

The curable resin composition may contain a curing agent. Examples of the curing agent include phenolic resins, polycarboxylic acids and anhydrides thereof, cyanate resins, active ester resins, maleimide compounds, alicyclic olefin polymers, and the like. The curing agents may be used alone in 1 kind or in combination of 2 or more kinds.

The curing agent is preferably compounded in such a manner that the ratio of a functional group capable of undergoing a thermosetting reaction, such as an epoxy group, of the thermosetting resin to a functional group in the curing agent capable of reacting with the functional group is 0.2 to 2 in terms of the ratio of the functional group of the curing agent to the functional group capable of undergoing a thermosetting reaction (equivalent ratio). When the ratio of the functional group of the curing agent to the functional group capable of undergoing the thermosetting reaction (equivalent ratio) is in the above range, roughening of the film surface in the desmear step can be prevented. More preferably, the ratio of the functional group of the curing agent to the functional group capable of undergoing a thermosetting reaction (equivalent ratio) is 0.2 to 1.5.

(curing accelerators)

The curable resin layer may contain a curing accelerator. The curing accelerator accelerates the thermosetting reaction and is used to further improve the properties such as adhesion, chemical resistance, and heat resistance. Specific examples of such a curing accelerator include: imidazole and derivatives thereof; guanamines such as 2, 4-diamino-6-methyl-1, 3, 5-triazine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea derivatives, melamine, and polyhydrazide; organic acid salts and/or epoxy adducts thereof; an amine complex of boron trifluoride; triazine derivatives such as ethyldiamino-s-triazine, 2, 4-diamino-s-triazine, and 2, 4-diamino-6-xylyl-s-triazine; amines such as trimethylamine, triethanolamine, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4, 6-tris (dimethylaminophenol), tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinyl phenol, polyvinyl phenol bromide, phenol novolac, and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine and the like; phosphonium salts such as tri-n-butyl (2, 5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4, 6-triphenylthiopyranium hexafluorophosphate and the like; styrene-maleic anhydride resin; an equimolar reaction product of phenyl isocyanate and dimethylamine, an equimolar reaction product of an organic polyisocyanate such as toluene diisocyanate or isophorone diisocyanate and dimethylamine, a conventionally known curing accelerator such as a metal catalyst. Among the curing accelerators, phosphonium salts are preferable because of the BHAST resistance. The curing accelerators may be used singly or in combination of 2 or more.

(photoreaction initiator)

The curable resin composition may contain a photoreaction initiator. The photoreaction initiator may be any one that can generate a radical, a base, an acid, or the like by irradiation with light to cure the curable resin. Examples of the photoreaction initiator include known and conventional compounds such as benzophenone-based, acetophenone-based, aminobenzophenone-based, benzoin ether-based, benzyl ketal-based, acylphosphine oxide-based, oxime ether-based, oxime ester-based, titanocene-based and the like. The photoreaction initiator preferably contains 1 or 2 or more species selected from the group consisting of oxime ester, α -aminoacetophenone acylphosphine oxide and titanocene.

Examples of the oxime ester photoreaction initiator include 1, 2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), and 2- (acetoxyiminomethyl) thioxanthen-9-one. The oxime ester type photoreaction initiator may be a compound having a plurality of oxime ester groups.

Examples of the α -aminoacetophenone-based photoreaction initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl) -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone.

Examples of the acylphosphine oxide-based photoreaction initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and the like.

Examples of the titanocene-based photoreaction initiator include bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.

The curable resin composition may contain a photoreaction initiator, a photoinitiator aid, and a sensitizer other than the above-described compounds, and examples thereof include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, xanthone compounds, tertiary amine compounds, and the like.

(inorganic Filler)

The curable resin composition may contain an inorganic filler. The inorganic filler is preferable to improve the properties of the cured product such as adhesion, mechanical strength, and linear expansion coefficient. As the inorganic filler, for example, a known and conventional inorganic filler such as barium sulfate, barium titanate, silica powder, fine-powder silica, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, zirconium phosphate, mica powder, or the like can be used. Here, the inorganic filler preferably contains at least any one of barium sulfate and silica.

The average particle diameter of the inorganic filler is preferably 0.1 to 20 μm. The average particle diameter can be determined by a laser diffraction particle size distribution measuring apparatus. Examples of the measuring apparatus using the laser diffraction method include Microtrac BEL (Nanotrac wave). Here, the average particle diameter refers to a concept including an average primary particle diameter and an average secondary particle diameter.

(organic solvent)

The curable resin composition may contain an organic solvent for composition preparation and viscosity adjustment. As the organic solvent, for example: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

(coloring agent)

The curable composition may contain a colorant. The colorant is not particularly limited, and known colorants such as red, blue, green, and yellow may be used, and any of pigments, dyes, and pigments may be used. Among them, the colorant preferably does not contain halogen from the viewpoint of reducing environmental load and influence on the human body.

Examples of The red colorant include monoazo colorants, disazo colorants, azo colorants, benzimidazolone colorants, perylene colorants, diketopyrrolopyrrole colorants, condensed azo colorants, anthraquinone colorants, quinacridone colorants, and The like, and specifically include those having a color index (c.i.; issued to The Society of dyers and colorists) number described below.

Examples of the monoazo-based red colorant include pigment red 1,2, 3,4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, and the like. Examples of the disazo red colorant include pigment red 37, 38, and 41. Further, examples of the monoazo lake-based red colorant include pigment red 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53: 1. 53: 2. 57: 1. 58: 4. 63: 1. 63: 2. 64: 1. 68, etc. Examples of the benzimidazolone-based red colorant include pigment red 171, 175, 176, 185, and 208. Examples of perylene red colorants include solvent red 135, 179, pigment red 123, 149, 166, 178, 179, 190, 194, and 224. Examples of the diketopyrrolopyrrole-based red colorant include pigment red 254, 255, 264, 270, and 272. Examples of the condensed azo red colorant include pigment reds 220, 144, 166, 214, 220, 221, and 242. Examples of the anthraquinone-based red colorant include pigment red 168, 177, 216, solvent red 149, 150, 52, 207, and the like. The quinacridone-based red colorant includes pigment reds 122, 202, 206, 207, and 209.

Examples of the blue colorant include phthalocyanine-based colorants and anthraquinone-based colorants, and examples of the Pigment-based colorants include compounds classified as pigments (pigments), and examples of the pigments include Pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 60, solvent blues 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used as dye systems. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound may be used.

Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based colorants, and examples of the anthraquinone-based yellow colorant include solvent yellow 163, pigment yellow 24, 108, 193, 147, 199, and 202. Examples of the isoindolinone yellow colorant include pigment yellows 110, 109, 139, 179, and 185. Examples of the condensed azo yellow colorant include pigment yellows 93, 94, 95, 128, 155, 166, and 180. Examples of the benzimidazolone-based yellow colorant include pigment yellow 120, 151, 154, 156, 175, 181, and the like. Further, examples of the monoazo-based yellow colorant include pigment yellow 1,2, 3,4, 5, 6, 9, 10, 12, 61, 62: 1. 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc. Examples of the disazo yellow colorant include pigment yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, and the like.

In addition, coloring agents such as violet, orange, brown, and black may be added. Specifically, pigment black 1,6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, c.i. pigment orange 1,5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, pigment brown 23, 25, carbon black, titanium oxide, and the like can be given.

[ use ]

The structure of the present invention is preferably used for forming a cured film of a printed wiring board, more preferably for forming a permanent protective film, and particularly preferably for forming an interlayer insulating layer, a cover layer, a solder resist, or a via filling (material). Further, the structure of the present invention can form a cured product having excellent film strength even when it is a thin film, and therefore, it can be suitably used for forming a pattern layer in a printed wiring board, for example, a package substrate (a printed wiring board used for a semiconductor package), which is required to be made thin. Further, the structural body of the present invention can also be suitably used for a flexible printed circuit board.

< description of the second embodiment >

< Structure >

The structure of the present invention includes a first film and a resin layer, and the first film and the resin layer satisfy specific conditions described below. In the present invention, a structure in which a resin layer having a small variation in thickness is formed on a first film can be obtained by allowing the first film and the resin layer to satisfy specific conditions described later.

The structure of the present invention will be described with reference to the drawings. Fig. 2 is a schematic cross-sectional view showing one embodiment of the structure of the present invention. As shown in fig. 2, the structure 1 includes a first film 10 and a resin layer 20 provided on one surface of the first film 10. Hereinafter, each constituent element constituting the structure of the present invention will be described.

[ first film ]

The first film has a function of supporting the resin layer of the structure, and is a film coated with a resin composition when the resin layer is formed. The first film may be peeled from the structure after curing the resin layer. Examples of the first film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene films and polypropylene films, fluororesin films such as polytetrafluoroethylene films, polyimide films, polyamideimide films, and films made of thermoplastic resins such as polystyrene films. Among these, polyester films and polyolefin films can be suitably used in terms of heat resistance, mechanical strength, handling properties, and the like. The surface of the first film on which the resin layer is provided may be subjected to a mold release treatment or a roughening treatment, or may be formed with a sputtering or an extra thin copper foil and an adhesive layer.

The thickness of the first film is 30 μm or more, preferably 35 μm or more and 125 μm or less. If the thickness of the first film is within the above numerical range, the occurrence of longitudinal wrinkles when tension is applied to the first film can be suppressed.

The first film has a trouser tear force of 0.1N or more, preferably 0.15N or more and 2N or less, and more preferably 0.2N or more and 1.5N or less. When the trouser tear force of the first film is within the above numerical range, wrinkles are less likely to occur, and variations in the thickness of the resin layer formed on the first film can be suppressed.

In the present invention, the trouser tear force of the first film is measured in accordance with JIS K7128-1: 1998 was measured under the following measurement conditions using a tensile tester (EZ-SX, manufactured by Shimadzu corporation).

(measurement conditions)

Temperature and humidity of the laboratory: 23 +/-2 ℃ and 50 +/-15 percent

Test piece size: 150mm x 50mm

Cut length in the center of the test piece: 75 +/-1 mm

Test speed: 200mm/min

Distance between the grips of the test piece: 75mm

The trouser tear force of the first film can be adjusted to a desired range by adjusting the kind of raw material of the first film, the stretch ratio at the time of film production, the thickness of the film, the breaking strength of the film, the heat shrinkage rate of the film, and the like.

In the structure of the present invention, the first film is preferably a film having a thickness variation of ± 10% or less, because the film thickness can be easily controlled by applying the resin layer without variation. More preferably ± 5% or less.

The variation in the thickness of the first film was measured as follows. That is, a sample was cut 40mm in the MD from a position 1m in the MD from the film end of the first film. For the measurement sample, 25 points were measured at 20mm intervals in the TD direction from a position 15mm from the end of the film using an automatic measurement type film thickness meter (TOF-J, manufactured by shanwen electric corporation). The maximum value, the minimum value and the average value were calculated from the measurement results at 25 points, and the thickness variation was calculated from the difference between the maximum value and the minimum value according to the following formula.

Deviation (%) of thickness ═ (max-min)/average × 100

[ resin layer ]

The resin layer is a curable resin layer formed on the first film of the structure. The curable resin layer is a dried coating film obtained by drying a liquid curable resin composition, and may be a thermosetting resin layer that is cured by heating, a photocurable resin layer that is cured by light irradiation, or a thermosetting photocurable resin layer that is cured by heating and is cured by light irradiation.

The thickness of the resin layer is 50 μm or more, preferably 50 μm or more and 200 μm or less. If the thickness of the resin layer is within the above numerical range, a large-sized member can be sealed.

In the present invention, the thickness of the resin layer is measured by the following method.

A measurement sample was obtained by cutting 40mm in the MD from a position 10m in the MD from the end of the coating film (resin layer) of the structure. For the measurement sample, 25 points were measured at 20mm intervals in the TD direction from a position 15mm away from the end of the coating film (resin layer) using an automatic measurement type film thickness meter (TOF-J, manufactured by shanwen electric corporation). The average value calculated from the measurement results of 25 points was taken as the thickness of the resin layer.

(curable resin composition)

The curable resin composition preferably contains a curable resin and a curing agent, and may further contain other components. The curable resin composition preferably contains at least one of a thermosetting resin and a photocurable resin as a curable resin.

(thermosetting resin)

The thermosetting resin is as described in detail in the first embodiment. Among the epoxy compounds, from the viewpoint of optimizing each of the fracture point strength, the thermal expansion coefficient and the storage modulus of the cured coating film, a bisphenol a type epoxy resin, a dicyclopentadiene type epoxy resin and a phenol novolac type epoxy resin are preferably used, more preferably 2 or more of them are used in combination, and still more preferably 3 of them are used in combination.

(Photocurable resin (radical polymerization))

The photocurable resin (radical polymerization) is as described in detail in the first embodiment.

(Photocurable resin (cationic polymerization))

The photocurable resin (cationic polymerization) is as described in detail in the first embodiment.

(alkali-soluble resin)

The curable resin composition may contain an alkali-soluble resin. The alkali-soluble resin is as described in detail in the first embodiment.

(thermoplastic resin)

In order to improve the mechanical strength of the obtained cured coating film, the curable resin composition may further contain a thermoplastic resin. The thermoplastic resin is as described in detail in the first embodiment.

(curing agent)

The curable resin composition may contain a curing agent. The curing agent is as specifically described in the first embodiment.

(curing accelerator)

The curable resin layer may contain a curing accelerator. The curing accelerator is as specifically described in the first embodiment.

(photoreaction initiator)

The curable resin composition may contain a photoreaction initiator. The photoreaction initiator is as described in detail in the first embodiment.

(inorganic Filler)

The curable resin composition may contain an inorganic filler. The inorganic filler is as described in detail in the first embodiment.

(organic solvent)

The curable resin composition may contain an organic solvent for composition preparation and viscosity adjustment. The organic solvent is as described in detail in the first embodiment.

(coloring agent)

The curable composition may contain a colorant. The colorant is as described in detail in the first embodiment.

(second film)

The structure of the present invention may comprise a second film. The second film is provided on the surface of the resin layer of the structure opposite to the first film for the purpose of preventing dust and the like from adhering to the surface of the resin layer and improving workability. The second film may be peeled from the resin layer before being attached to the substrate in use. As the second film, for example, a film made of a thermoplastic resin exemplified in the above-described first film can be used. Among these, polyester films and polyolefin films are preferable from the viewpoints of heat resistance, mechanical strength, handling properties, and the like. The surface of the second film on which the resin layer is provided may be subjected to a mold release treatment.

The thickness of the second film is not particularly limited and may be appropriately selected depending on the application. The thickness of the second film is preferably 10 μm to 100 μm, more preferably 15 μm to 50 μm, from the viewpoints of mechanical strength, handling properties, and the like.

[ use ]

The structure of the present invention can be preferably used for sealing and protecting applications for SAW filters. In addition to the above-described applications, the cured film is preferably formed on a printed wiring board, more preferably a permanent protective film, and particularly preferably formed on an interlayer insulating layer, a cover lay, a solder resist, or a filling (material) for filling holes. Further, the structure of the present invention can form a cured product having excellent film strength even when it is a thin film, and therefore, it can be suitably used for forming a pattern layer in a printed wiring board, for example, a package substrate (a printed wiring board used for a semiconductor package), which is required to be made thin. Further, the structural body of the present invention can also be suitably used for a flexible printed circuit board.

[ electric and electronic Components ]

The electric/electronic component of the present invention includes the printed wiring board. The electrical/electronic component of the present invention can be used for various electrical devices known in the art. Among them, a SAW filter is preferable.

Examples of the base material include a printed circuit board, an LTCC (low temperature co-fired ceramic) substrate (hereinafter also referred to as a low temperature co-fired ceramic substrate), a ceramic substrate, a silicon substrate, and a metal substrate. Examples of the electric and electronic components include sensors, MEMS, and SAW chips. Among them, a pressure sensor, a vibration sensor, and a SAW chip can be suitably used, and a SAW chip is particularly preferable.

When the thermosetting resin composition is dried to form a film, the bonding to the substrate is preferably performed under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, when a substrate on which components are mounted is used, even if there are irregularities, the substrate is in close contact with the irregularities, so that air bubbles are not mixed in, and the sealing property of the electric/electronic components is improved. The pressurizing condition is preferably about 0.1MPa to 2.0MPa, and the heating condition is preferably 40 ℃ to 120 ℃.

The curing after the application of the thermosetting resin composition can be carried out by a hot air circulation type drying oven, an IR oven, a hot plate, a convection oven, or the like (a method of bringing hot air in a drying machine into convection contact by using a device having a heat source of an air heating system using steam and a method of blowing the hot air to a support body by a nozzle). Among them, a hot air circulation drying furnace is preferably used in view of curability. For example, the cured product can be formed by performing the heating of the 1 st stage at 80 to 120 ℃, preferably 90 to 110 ℃ for 10 to 60 minutes, preferably 20 to 40 minutes, and then performing the heat curing of the 2 nd stage at 180 to 220 ℃, preferably 190 to 210 ℃ for 30 to 120 minutes, preferably 50 to 70 minutes. The 2-stage curing is preferable in that generation of bubbles during curing can be suppressed. Specifically, by volatilizing the residual solvent component in the 1 st stage, the generation of bubbles during main curing can be suppressed. Then, curing is performed at a higher temperature in the 2 nd stage, whereby curing can be completed.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In the following description, "part" and "%" are based on mass unless otherwise specified.

< embodiment of the first mode >

< preparation example A of curable resin composition >

(compounding example A1)

The solvent shown in formulation example A1 in Table 1 below was charged into a container, heated to 50 ℃ to make the solvent nonvolatile, and each epoxy resin was added thereto and sufficiently stirred to dissolve it. Thereafter, the additive and the filler were added, and the mixture was kneaded by a three-roll mill, and further, the curing agent, the curing accelerator, and another resin were added and sufficiently stirred by a stirrer, thereby obtaining a curable resin composition.

(blending example A2)

The respective components were compounded according to the formulation shown in compounding example a2 of table 1 below, and dispersed by a three-roll mill to obtain a curable resin composition.

(compounding example A3)

A curable resin composition was obtained in the same manner as in compounding example 1 except that the formulation was changed to the formulation shown in compounding example a3 shown in table 1 below.

[ Table 1]

In table 1, the mixing amounts of the respective components are based on parts by mass.

*1: JER828 manufactured by Mitsubishi chemical corporation

*2: HP-7200L manufactured by DIC corporation

*3: EPICLON N-740, manufactured by DIC corporation

*4: ST-6100 manufactured by Mitsubishi chemical corporation

*5: HP-4032 manufactured by DIC corporation

*6: HF-4M manufactured by Minghe chemical Co., Ltd

*7: manufactured by Nagase chemteX, Teisan Resin SG-P3 × 8: YX6954BH30, manufactured by Mitsubishi chemical corporation

*9: 2E4MZ, manufactured by four chemical industries, Ltd

*10: KBM-403 manufactured by shin-Etsu chemical Co., Ltd

*11: FB-7SDX manufactured by Denka corporation

*12: SO-C2, manufactured by Admatechs corporation

*13: carbon black

*14: c.i. pigment yellow 147

*15: phthalocyanine Blue 5380 Fastogen Blue, available from DIC corporation

*16: diethylene glycol monoethyl ether acetate

*17: cyclohexanone

Examples A1 to 7 and comparative examples A1 to 4

< production of Structure >

In order to produce the structure, the following films were prepared.

Film A: appearance: no luster, material quality: PET, thickness 38 μm, tensile strength in TD direction 215MPa, and tensile strength in MD direction 243MPa

Film B: appearance: lustrous and material quality: PET, thickness of 50 μm, tensile strength in TD direction of 235MPa, and tensile strength in MD direction of 185MPa

Film C: appearance: no luster, material quality: PP, thickness of 16 μm, tensile strength in TD direction of 250MPa, and tensile strength in MD direction of 120MPa

Film D: appearance: lustrous and material quality: PET, thickness of 38 μm, tensile strength in TD direction of 260MPa, and tensile strength in MD direction of 270MPa

Film E: appearance: lustrous and material quality: PET, thickness 38 μm, tensile strength 225MPa in TD direction, and tensile strength 205MPa in MD direction

Next, in each of examples and comparative examples, a 3-layer structure was obtained by combining the first film described in table 2, the resin layer (thermosetting resin layer) using the curable resin composition, and the second film. Specifically, the curable resin composition obtained above was applied to the first film using a bar coater so that the film thickness of the resin layer was 100 μm after drying. Then, the film is dried in a hot air circulation type drying furnace at 85 ℃ for 5 to 15 minutes so that the residual solvent amount is 1.0 to 4.0%, thereby forming a resin layer on the first film. Subsequently, a second film was attached to the surface of the dried coating film by a roll laminator at a set temperature of 90 ℃ and a pressure of 0.15MPa, to obtain a 3-layer structure.

< determination of trouser tear force >

For the film prepared above, the film was measured according to JIS K7128-1: 1998 "tear Strength test method for Plastic-films and sheets-first part: the trouser tear force was measured under the following conditions using a tensile tester (EZ-SX, manufactured by Shimadzu corporation). However, regarding the measurement direction, only the machine direction (MD direction) is measured regardless of the presence or absence of anisotropy based on the direction. The tear strength was averaged approximately for the remaining 50mm, except for 20mm from the start of tearing and 5mm from the end of tearing. The measurement results are shown in Table 2.

(measurement conditions)

Temperature and humidity of the laboratory: 23 +/-2 ℃ and 50 +/-15 percent

Test piece size: 150mm x 50mm

Cut length in the center of the test piece: 75 +/-1 mm

Number of samples: 5

Test speed: 200mm/min

Distance between the grips of the test piece: 75mm

< measurement of haze >

The film prepared above was measured for haze using a haze meter (NDH 7000II, manufactured by japan electro-chromic co., ltd.) according to ASTM D1003. The measurement results are shown in Table 2.

< measurement of L a b >

The first film and the second film of the structure obtained above were measured for L, a, and b using a spectrophotometer (CM-2600 d; manufactured by konica minolta corporation) under the following conditions. L, a, b of the first film are measured from the first film side of the structure. L, a, b of the second film are measured from the second film side of the structure. The measurement results are shown in Table 2.

(measurement conditions)

Number of samples: n is 3

Reflection mode

Specular reflection light processing

Measurement of diameter: SAV (3mm)

UV conditions: 100% full of

Visual field: 10 degree

65 degree of incident light

Measurement method: SCE (except for specular component)

Substrate: black lining paper (L value: 27.3, a value 0.7, b value 2.0)

< Presence or absence of film marks >

The structure obtained above was peeled from the second film side at an angle of 180 degrees and a speed of 2 cm/sec, and the appearance of the resin layer at this time was visually confirmed. The film mark of the resin layer was evaluated according to the following criteria, and the evaluation results are shown in table 3.

(evaluation criteria)

Very good: the resin layer had no film mark.

O: the resin layer has a film mark having no influence on use.

X: the resin layer has a film mark that greatly influences in use.

< visibility of appearance of Structure >

The visibility of the appearance was visually confirmed from the second film side (front surface) to the first film side (back surface) of the structure obtained above. The visibility of the appearance of the structure was evaluated according to the following criteria, and the evaluation results are shown in table 3.

(evaluation criteria)

Very good: the front and back of the structure are easily distinguished.

O: the front and back of the structure can be distinguished.

X: the front and back of the structure cannot be distinguished.

As is clear from table 3, the structure of the example of the first embodiment of the present application can easily distinguish between the front surface and the back surface, and the resin layer can be made less likely to have film marks when the second film is peeled.

< example of the second mode >

< preparation example B of curable resin composition >

(compounding example B1)

The solvent shown in compounding example B1 in Table 4 below was charged into a container, heated to 50 ℃ so as to make the solvent nonvolatile, and each epoxy resin was added thereto and sufficiently stirred to dissolve it. Thereafter, the additive and the filler were added, and the mixture was kneaded by a three-roll mill, and further, the curing agent, the curing accelerator, and another resin were added and sufficiently stirred by a stirrer, thereby obtaining a curable resin composition.

(compounding example B2)

The respective components were compounded according to the formulation shown in compounding example B2 of table 4 below, and dispersed by a three-roll mill to obtain a curable resin composition.

[ Table 4]

In table 4, the blending amount of each component is based on parts by mass.

*18: JER828 manufactured by Mitsubishi chemical corporation

*19: HP-7200L manufactured by DIC corporation

*20: EPICLON N-740, manufactured by DIC corporation

*21: ST-6100 manufactured by Mitsubishi chemical corporation

*22: HP-4032 manufactured by DIC corporation

*23: HF-4M manufactured by Minghe chemical Co., Ltd

*24: teisan Resin SG-P3 (solid content: 15% by mass), manufactured by Nagase chemteX K.K.)

*25: YX6954BH30 (solid content: 30% by mass), manufactured by Mitsubishi chemical corporation

*26: 2E4MZ, manufactured by four chemical industries, Ltd

*27: KBM-403 manufactured by shin-Etsu chemical Co., Ltd

*28: FB-7SDX manufactured by Denka corporation

*29: carbon black

*30: diethylene glycol monoethyl ether acetate

*31: cyclohexanone

Examples B1 to 7 and comparative examples B1 to 4

< production of Structure >

To manufacture the structure, the following first film was prepared.

Film a: the material is as follows: PET, 50 μm thick, 186MPa tensile strength in MD direction with release agent on one side, 130% elongation in MD direction

Film B: the material is as follows: PET, 38 μm thick, tensile strength in MD direction 206MPa with release agent on one side, and elongation in MD direction 120%

Film C: the material is as follows: PI (polyimide), thickness of 50 μm, tensile strength of 300MPa in MD direction, and elongation of 85% in MD direction

Film D: the material is as follows: PP, 30 μ M thick, adhesive layer on one side, tensile strength M80Pa in MD direction, and elongation 225% in MD direction

Film E: the material is as follows: PP, thickness 15 μm, tensile strength in MD 100MPa, and elongation in MD 150%

Film G: the material is as follows: PET, thickness 125 μm, tensile strength 225MPa in MD direction, and elongation 125% in MD direction

Film H: the material is as follows: PET, thickness of 25 μm, tensile strength in MD of 186MPa, and elongation in MD of 130%

Next, in each of examples and comparative examples, a structure was obtained by combining the first film described in table 5 with a resin layer (curable resin layer) using the curable resin composition described above. Specifically, the curable resin composition obtained above was applied to a first film having a tension of 100N/m in the MD direction by a die coater, and then dried at 100 ℃ for 3.5 minutes to form a curable resin layer, thereby obtaining a structure.

< measurement of thickness of first film and variation thereof >

The first film prepared above was cut 40mm in the MD from a position 1m in the MD from the film end to be used as a measurement sample. For the measurement sample, 25 points were measured at 20mm intervals in the TD direction from a position 15mm from the end of the film using an automatic measurement type film thickness meter (TOF-J, manufactured by shanwen electric corporation). The maximum value, the minimum value and the average value were calculated from the measurement results at 25 points, and the thickness variation was calculated from the difference between the maximum value and the minimum value according to the following formula. The calculation results are shown in Table 5.

Thickness deviation (%) - (max-min)/average × 100

< determination of trouser tear force >

For the film prepared above, the film was measured according to JIS K7128-1: 1998, the trouser tear strength was measured under the following conditions using a tensile tester (EZ-SX, manufactured by Shimadzu corporation). The approximate average of the tear strength was determined for the remaining 50mm, except for 20mm from the start of tearing and 5mm from the end of tearing. The measurement results are shown in Table 5.

(measurement conditions)

Temperature and humidity of the laboratory: 23 +/-2 ℃ and 50 +/-15 percent

Test piece size: 150mm x 50mm

Cut length in the center of the test piece: 75 +/-1 mm

Number of samples: 5

Test speed: 200mm/min

Distance between the grips of the test piece: 75mm

< measurement of thickness of resin layer and variation thereof >

The structure thus obtained was cut 40mm in the MD from a position 10m away from the end of the dry coating film (resin layer) in the MD to obtain a measurement sample. For the measurement sample, 25 points were measured at 20mm intervals in the TD direction from a position 15mm away from the end of the dried coating film (resin layer) using an automatic measurement type film thickness meter (TOF-J, manufactured by shanwen electric corporation). The maximum value, minimum value and average value were calculated from the measurement results of 25 points. The average values are shown in Table 5.

Further, the thickness variation was calculated from the difference between the maximum value and the minimum value according to the following formula, and evaluated according to the following criteria.

Deviation (%) of thickness ═ (max-min)/average × 100

(evaluation criteria)

Very good: the difference between the maximum value and the minimum value at 25 points is 5% or less with respect to the average value.

O: the difference between the maximum value and the minimum value at 25 points is more than 5% and 10% or less with respect to the average value.

X: the difference between the maximum and minimum values of the 25 points was more than 10% from the average value.

As can be seen from table 5, the resin layer of the structure of the example of the second embodiment of the present application has a thickness of 50 μm or more, but the variation in thickness is small.

Description of the symbols

1 Structure

10 first film

20 resin layer

30a second film.

Claims (11)

1. A structure comprising a first film, a resin layer and a second film in this order,

the difference between the trouser tear force of the first film and the trouser tear force of the second film is less than-0.05N or more than +0.05N,

the difference between the haze of the first film and the haze of the second film is-5% or less or + 5% or more.

2. A structure comprising a first film, a resin layer and a second film in this order,

the difference between the trouser tear force of the first film and the trouser tear force of the second film is less than-0.05N or more than +0.05N,

the difference between the L, a, b values measured from the first membrane side of the structure and the L, a, b values measured from the second membrane side of the structure satisfies at least one of the following conditions (i) to (iii),

(i) the difference of L is less than-0.1 or more than + 0.1;

(ii) the difference of a is less than-0.1 or more than + 0.1;

(iii) the difference of b is less than-1 or more than + 1.

3. The structure of claim 1 or 2, wherein the second film has a trouser tear force less than the trouser tear force of the first film.

4. A structure according to any one of claims 1 to 3, wherein the resin layer is a curable resin layer.

5. A structure as claimed in any of claims 1 to 4, wherein the first film is selected from polyester films and polyolefin films.

6. A structure as claimed in any of claims 1 to 5, wherein the second film is selected from polyester films and polyolefin films.

7. A structure comprising a first film and a resin layer, characterized in that,

the first film has a thickness of 30 [ mu ] m or more,

the trouser tear force of the first film is 0.10N or more,

the thickness of the resin layer is 50 [ mu ] m or more,

the resin layer is a curable resin layer.

8. The structure according to claim 7, wherein the curable resin layer comprises a thermosetting resin and a curing agent.

9. The structure of claim 8, wherein the thermosetting resin is an epoxy compound.

10. The structure of any one of claims 7 to 9, wherein the first film is selected from the group consisting of polyester films, polyolefin films, and polyimide films.

11. The structure according to any one of claims 7 to 10, wherein a variation in thickness of the first film is ± 10% or less.

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